Molding material and method for producing resin molded body using same

Patent metadata

Field	Value
Publication number	US-11623975-B2
Application number	US-201816481117-A
Country	US
Kind code	B2
Filing date	Jan 26, 2018
Priority date	Jan 27, 2017
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

A molding material including a resin material that has a graft chain containing constituent units derived from a fluorine-containing compound and a non-fluorinated compound. The graft chain thereof may be formed, for example, using ionizing radiation.

First claim

The invention claimed is:

1. A molding material comprising a resin material that has a graft chain containing constituent units derived from a fluorine-containing compound and a non-fluorinated compound;
wherein
a depth of the graft chain is 1 to 95% of the molding material,
the molding material is in the shape of a pellet, and
the resin material is in the shape of a pellet.

2. The molding material according to claim 1 , wherein the fluorine-containing compound comprises at least one selected from the group consisting of a fluorine-containing acrylate ester represented by formula (1):

wherein
X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group, a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
X 1 and X 2 , independently of each other, represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a —CH 2 CH 2 N(R 1 )SO 2 — group, or a —CH 2 CH(OY 1 )CH 2 — group;
R 1 is an alkyl group having 1 to 4 carbon atoms;
Y 1 is a hydrogen atom or an acetyl group; and
Rf 8 is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 6 carbon atoms,
a compound represented by Rf j CH═CH 2 , wherein Rf j is a perfluoroalkyl group, and a perfluoroolefin.

3. A method for producing a resin molded body, comprising:
contacting a resin material before the irradiation with ionizing radiation with a fluorine-containing compound and/or a non-fluorinated compound; and
irradiating the resin material with radiation to introduce a graft chain containing constituent units derived from the fluorine-containing compound and constituent units derived from the non-fluorinated compound to the resin material to obtain a molding material and molding the obtained molding material;

wherein
the molding material is in the shape of a pellet, and
the resin material is in the shape of a pellet.

4. The method according to claim 3 , wherein the fluorine-containing compound comprises at least one selected from the group consisting of a fluorine-containing acrylate ester represented by formula (1):

wherein
X is a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a CFX 1 X 2 group, a cyano group, a linear or branched fluoroalkyl group having 1 to 21 carbon atoms, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group;
X 1 and X 2 , independently of each other, represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
Y is an aliphatic group having 1 to 10 carbon atoms, an aromatic group or cycloaliphatic group having 6 to 10 carbon atoms, a —CH 2 CH 2 N(R 1 )SO 2 — group, or a —CH 2 CH(OY 1 )CH 2 — group;
R 1 is an alkyl group having 1 to 4 carbon atoms;
Y 1 is a hydrogen atom or an acetyl group; and
Rf 8 is a linear or branched fluoroalkyl group or fluoroalkenyl group having 1 to 6 carbon atoms,
a compound represented by Rf j CH═CH 2 , wherein Rf j is a perfluoroalkyl group, and
a perfluoroolefin.

5. A method for producing a resin molded body, comprising:
the molding material according to claim 1 is molded by a molding method including heating treatment to segregate the graft chain on a surface of the resin molded body.

6. The molding material according to claim 1 , wherein
the non-fluorinated compound is a group selected from a compound having a moiety reactive with radicals, a compound in which a part of the molecule or molecular chain is desorbed to ionize, or a compound having a moiety to be intermediate active species.

7. The method according to claim 3 , wherein
the non-fluorinated compound is a group selected from a compound having a moiety reactive with radicals, a compound in which a part of the molecule or molecular chain is desorbed to ionize, or a compound having a moiety to be intermediate active species.

8. The molding material according to claim 1 , wherein the graft chain is present to a maximum depth of 20 mm from a surface of the molding material.

9. The molding material according to claim 1 , wherein the fluorine-containing compound is represented by one or more of formula (1) to (6) below:

wherein:
Rf 9 represents a perfluoroalkyl group having 1 to 6 carbon atoms;
R 91 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
R 92 represents an alkylene group having 1 to 10 carbon atoms;
R 93 represents a hydrogen atom or a methyl group;
n9 represents an integer of 1 to 10; and
Ar represents an aryl group optionally having a substituent.

10. The molding material according to claim 1 , wherein the fluorine-containing compound contains one or more the following compounds:
CF 3 (CF 2 ) 5 (CH 2 )OCOCH═CH 2 ,
CF 3 (CF 2 ) 5 (CH 2 )OCOC(CH 3 )═CH 2 ,
CF 3 (CF 2 ) 7 (CH 2 )OCOCH═CH 2 ,
CF 3 (CF 2 ) 7 (CH 2 )OCOC(CH 3 )═CH 2 ,
(CF 3 ) 2 CF(CF 2 ) 3 (CH 2 ) 2 OCOCH═CH 2 ,
CF 3 (CF 2 ) 3 (CH 2 ) 2 OCOC(CH 3 )═CH 2 ,
CF 3 (CF 2 ) 3 (CH 2 ) 2 OCOCH═CH 2 ,
CF 3 (CF 2 ) 5 (CH 2 ) 2 OCOC(CH 3 )═CH 2 ,
CF 3 (CF 2 ) 5 (CH 2 ) 2 OCOCH═CH 2 ,
CF 3 CF 2 (CH 2 ) 2 OCOCH═CH 2 ,
CF 3 (CF 2 ) 3 SO 2 N(CH 3 )(CH 2 ) 2 OCOCH═CH 2 ,
CF 3 (CF 2 ) 3 SO 2 N(C 2 H 5 )(CH 2 ) 2 OCOC(CH 3 )═CH 2 ,
(CF 3 ) 2 CF(CF 2 ) 3 CH 2 CH(OCOCH 3 )CH 2 OCOC(CH 3 )═CH 2 , or
(CF 3 ) 2 CF(CF 2 ) 3 CH 2 CH(OH)CH 2 OCOCH═CH 2 .

11. The molding material according to claim 1 , wherein the non-fluorinated compound contains one or more of the following compounds:
(meth)acrylic monomers in which an alkyl group having 1 to 20 carbon atoms is bonded to an ester terminal, vinylnorbornene, styrene, vinyl chloride, 1-hexene, 1-octene, 1-decene, 1-dodecene, isobutene, pentene, heptene, nonene, acetophenone, benzoin isopropyl ether, benzophenone, Michler's ketone, chlorothioxanthone, isopropylthioxanthone, benzyl dimethyl ketal, acetophenone diethyl ketal, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-phenylpropane and derivatives thereof, acetophenone O-benzoyloxime, nifedipine, 1,2-bis(4-methoxyphenyl)-2-oxoethyl cyclohexylcarbamate, 2-nitrobenzyl cyclohexylcarbamate, 2-(9-oxoxanthen-2-yl)propionic acid, 1,5,7-triazabicyclo[4.4.0]dec-5-ene and derivatives thereof, ethyl alcohol, isopropyl alcohol, toluene, xylene, hexane, cyclohexane, benzene, tetrahydrofuran, onium salts, sulfonium salts, or a cationic polymerization initiator that produces a Broensted acid or a Lewis acid.

12. The method according to claim 3 , wherein the fluorine-containing compound is represented by one or more of formula (1) to (6) below:

wherein:
Rf 9 represents a perfluoroalkyl group having 1 to 6 carbon atoms;
R 91 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms;
R 92 represents an alkylene group having 1 to 10 carbon atoms;
R 93 represents a hydrogen atom or a methyl group;
n9 represents an i

Assignees

• Univ Osaka
• Daikin Ind Ltd

Inventors

• Oshima Akihiro
• Satoh Kazuyuki
• Usugaya Mitsuhiro
• Ohmukai Yoshikage
• Shiotani Yuko

Classifications

• C08J2323/06

  Polyethene · CPC title

• C08F255/02

  on to polymers of olefins having two or three carbon atoms · CPC title

• C08J3/28

  Treatment by wave energy or particle radiation · CPC title

• C08J3/126 Primary

  Polymer particles coated by polymer, e.g. core shell structures · CPC title

• C08F255/08

  on to polymers of olefins having four or more carbon atoms · CPC title