Method for manufacturing laminate

Patent metadata

Field	Value
Publication number	US-10682669-B2
Application number	US-201616066167-A
Country	US
Kind code	B2
Filing date	Dec 27, 2016
Priority date	Dec 28, 2015
Publication date	Jun 16, 2020
Grant date	Jun 16, 2020

Abstract

The present invention provides a method for manufacturing a laminate that exhibits visible light transparency and ultraviolet light shielding properties while maintaining an extremely high degree of scratch resistance, and that has all the necessary weather resistance and durability properties for withstanding long-term outdoor exposure. This method for manufacturing a laminate having the abovementioned properties includes: (1) using active energy rays to cure, on an organic resin substrate, an acrylic silicone resin composition having an inorganic component percentage X of 0.2 to 0.8 to form an intermediate layer, (2) dry-etching the surface of the intermediate layer obtained at step (1) using a non-oxidizing gas plasma of a plasma irradiation amount Y correlated with the inorganic component percentage X; and (3) plasma-polymerizing an organosilicon compound to form a hard coat layer on the surface of the intermediate layer obtained at step (2).

First claim

The invention claimed is:

1. A method for manufacturing a laminate, comprising:
(1) curing an acrylic silicone resin composition by an active energy ray on an organic resin substrate to form an intermediate layer, wherein the acrylic silicone resin composition is an acrylic silicone resin composition containing, with respect to 100 parts by mass of the following Component (i), from 100 to 500 parts by mass of the following Component (ii), from 10 to 150 parts by mass of the following Component (iii), from 5 to 50 parts by mass of the following Component (iv), from 200 to 1000 parts by mass of the following Component (v), from 0 to 500 parts by mass of the following Component (vi), and from 0 to 500 parts by mass of the following Component (vii), and an inorganic component percentage X value obtained by dividing total parts by mass of the following Components (ii), (iii), (vi), and (vii) by total parts by mass of the following Components (i) to (vii) is from 0.2 to 0.8;
(2) dry etching a surface of the intermediate layer obtained in step (1) with a non-oxidizing gas plasma so as to satisfy the following Formulae 1 and 2:
Y> 5/3×(10× X+ 13)  Formula 1:

Y< 275× X− 30,  Formula 2:

wherein Y represents a plasma irradiation dose (J/cm 2 ); then
(3) plasma polymerizing an organosilicon compound on the surface of the intermediate layer obtained in step (2) to form a hard coat layer:
Component (i): a vinyl-based polymer represented by the following general formula (I):
Poly-[( A ) a -co-( B ) b -co-( C ) c ]  (I)

wherein
‘A’, ‘B’, and ‘C’ each independently represent a vinyl-based monomer unit;
square brackets and -co- represent being a random copolymer;
‘a’, ‘b’, and ‘c’ represent a mole fraction;
‘A’ represents a vinyl-based monomer unit having an alkoxysilyl group, and ‘a’ represents a mole fraction of the monomer unit A and accounts for from 1 to 50% by mass of a total amount of the vinyl-based polymer;
‘B’ represents a ultraviolet-absorbing vinyl-based monomer unit, and ‘b’ represents a mole fraction of the monomer unit B and accounts for from 5 to 40% by mass of the total amount of the vinyl-based polymer; and
‘C’ represents another monomer unit copolymerizable with the vinyl-based monomer units A and B, and ‘c’ represents a mole fraction of the monomer unit C and accounts for [100−(content of monomer unit A)−(content of monomer unit B)]% by mass of the total amount of the vinyl-based polymer);

Component (ii): a hydrolytic condensate obtained by (co-) hydrolysis and condensation of at least one selected from alkoxysilanes represented by the following general formula (II) and partial hydrolysates thereof:
R 1 m R 2 n Si(OR 3 ) 4-m-n   (II)

wherein
R 1 and R 2 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may be unsubstituted or may have a vinylic polymerizable group, the substituents optionally bonding to each other;
R 3 represents an alkyl group having 1 to 3 carbon atoms; and
‘m’ and ‘n’ each independently represent 0 or 1, and
‘m+n’ represent 0, 1, or 2;

Component (iii): core-shell type tetragonal titanium oxide solid-solution fine particles having a core of tetragonal titanium oxide fine particles containing tin and manganese in the form of solid solution and a shell of silicon oxide outside the core, wherein, as measured by a dynamic light scattering method, the core fine particles have a 50% cumulative distribution diameter of 30 nm or less on a volumetric basis, the core-shell type tetragonal titanium oxide solid-solution have a 50% cumulative distribution diameter of 50 nm or less on a volumetric basis, the solid solution content of tin expressed by a mole ratio of titanium to tin (Ti/Sn) is from 10 to 1,000, and the solid solution content of manganese expressed by a mole ratio of titanium to manganese (Ti/Mn) is 10 to 1,000;
Component (iv): a polycarbonate-based and/or polyester-based urethane-modified vinyl-based polymer, provided that Component (iv) is not Component (i);
Component (v): a vinyl-based polymerizable monomer that has no alkoxysilyl group and that does not form any polymer and/or any condensate before irradiation by the active energy ray, provided that Component (v) is not Components (i) and (ii);
Component (vi): a siloxane acrylate represented by the following general formula (IIIa):

wherein
R 1 , R 2 , R 3 , and R 4 each independently represent a hydrogen atom or a methyl group;
Y 1 , Y 2 , Y 3 and Y 4 each independently represent an alkylene group having 1 to 10 carbon atoms; and
‘n’ represents an integer of from 1 to 10; and

Component (vii): an inorganic oxide, provided that Component (vii) is not Component (iii).

2. The method according to claim 1 , wherein Component (vi) is contained in an amount of from 20 to 500 parts by mass with respect to 100 parts by mass of Component (i).

3. The method according to claim 1 , wherein the organosilicon compound is plasma polymerized by using a capacitively coupled plasma generator.

4. The method according to claim 1 , wherein the organic resin substrate is composed of a single layer.

5. The method according to claim 1 , wherein the organic resin substrate has a plurality of layers including a base resin and a cap layer that are co-extruded or laminated together.

6. The method according to claim 1 , wherein the hard coat layer has a thickness of from 3.5 to 20.0 μm.

7. The method according to claim 1 , wherein, by the dry etching at the step (2), the surface of the intermediate layer has a water contact angle of 40° or less and a surface roughness of from 0.7 to 5 nm.

8. The method according to claim 1 , wherein the laminate has an acceptance value of 97% or higher in a tape adhesion test based on ASTM D3359, Method B and a tape adhesion test according to ASTM D870 using ion exchanged water kept at 65° C. for 3 days, and has a delta haze value of less than 2% in a Taber abrasion test at 1000 cycles based on ASTM D1044.

9. The method according to claim 1 , wherein a composition of the hard coat layer is changed continuously from an interface with the intermediate layer to the surface of the hard coat layer in a thickness direction by continuously changing electric power to be input, an amount of an organosilicon gas to be introduced, and an amount of a carrier gas to be introduced during the plasma irradiation.

10. The method according to claim 1 , wherein the organosilicon compound used for the plasma polymerization has an average composition represented by the following Formula (A):
(SiH x O y R z ) n   Formula (A):

wherein
R represents a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxy group having 1 to 4 carbon atoms, an amino group, a methylamino group, a dimethylamino group, or a hydroxy group;
‘x’ represents from 0.5 to 2;
‘y’ represents from 0.1 to 1;
‘z’ represents from 0.5 to 1.5; and
‘n’ represents from 1 to 6.

11. The method according to claim 1 , wherein the acrylic silicone resin composition used for forming the intermediate layer contains an organic ultraviolet absorber and/or an organic ultraviolet stabilizer.

12. The method according to claim 1 , wherein the organic resin substrate is a polycarbonate resin substrate.

Assignees

• Shinetsu Chemical Co
• Teijin Ltd

Inventors

• Masuda Kohei
• Tanaka Masaki
• Yoda Takashi
• Ekinaka Tatsuya

Classifications

• C08J7/048

  Forming gas barrier coatings · CPC title

• C08J7/046

  Forming abrasion-resistant coatings; Forming surface-hardening coatings · CPC title

• C08J7/043

  Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50) · CPC title

• C08J7/042

  with two or more layers, where at least one layer of a composition contains a polymer binder · CPC title

• B05D3/141

  Plasma treatment · CPC title