Method for producing novel ali cyclic ester compound, novel alicyclic ester compound, (meth)acrylic copolymer produced by polymerizing said compound, and photosensitive resin composition using said copolymer

Patent metadata

Field	Value
Publication number	US-9994513-B2
Application number	US-201515117668-A
Country	US
Kind code	B2
Filing date	Feb 12, 2015
Priority date	Feb 14, 2014
Publication date	Jun 12, 2018
Grant date	Jun 12, 2018

Abstract

Provided are a resist and a compound for the resist improving the sensitivity, the resolution and the line edge roughness (LER) in a good balance without spoiling basic properties of a chemical amplification resist such as pattern shape, dry etching resistance, heat resistance and the like. Provided are a method for producing an alicyclic ester compound expressed by general formula (1), an alicyclic ester compound expressed by general formula (1), a (meth)acrylic copolymer obtained by polymerization of the alicyclic ester compound, and a photosensitive resin composition containing the (meth)acrylic copolymer. A method for producing an alicyclic ester compound expressed by general formula (1) includes reacting an adamantane compound expressed by general formula (2) with hydroxyalkylamine expressed by general formula (3) to produce an adamantaneamide compound expressed by general formula (4), and then reacting the adamantaneamide compound expressed by general formula (4) with (meth)acrylic acid.

First claim

The invention claimed is:

1. A method for producing an alicyclic ester compound expressed by general formula (1):

where R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 may be the same as, or different from, each other and independently represent a hydrogen atom, a hydroxyl group, a cyclic, linear or branched alkyl group having a carbon number of 1 to 10, an aryl group, a cycloalkyl group, an alkoxy group having a carbon number of 1 to 10, an aryloxy group, an acyloxy group having a carbon number of 2 to 6, or a halogen group, and R 4 represents a linear or branched alkylene group having a carbon number of 2 to 5;
the method comprising reacting an adamantane compound expressed by general formula (2) with hydroxyalkylamine expressed by general formula (3) to produce an adamantaneamide compound expressed by general formula (4), and then reacting the adamantaneamide compound expressed by general formula (4) with (meth)acrylic acid:

where R 2 and R 3 are the same as those in chemical formula (1);
[Chemical formula 3]
H 2 N—R 4 —OH  (3)

where R 4 is the same as that in chemical formula (1);

where R 2 , R 3 and R 4 are the same as those in chemical formula (1).

2. The method for producing an alicyclic ester compound according to claim 1 , the method comprising the step of heating the adamantane compound expressed by general formula (2) and the hydroxyalkylamine expressed by general formula (3) to cause dehydration condensation to produce the adamantaneamide compound expressed by general formula (4) as shown below:

3. A method for producing an alicyclic ester compound expressed by general formula (1):

where R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 may be the same as, or different from, each other and independently represent a hydrogen atom, a hydroxyl group, a cyclic, linear or branched alkyl group having a carbon number of 1 to 10, an aryl group, a cycloalkyl group, an alkoxy group having a carbon number of 1 to 10, an aryloxy group, an acyloxy group having a carbon number of 2 to 6, or a halogen group, and R 4 represents a linear or branched alkylene group having a carbon number of 2 to 5;
the method comprising reacting an adamantane compound expressed by general formula (2) with aminoalkyl (meth)acrylate expressed by general formula (5) to produce the alicyclic ester compound expressed by general formula (1):

where R 2 and R 3 are the same as those in chemical formula (1);

where R 1 and R 4 are the same as those in chemical formula (1).

4. The method for producing an alicyclic ester compound according to claim 3 , wherein the reaction, expressed by the following formula, of the adamantane compound expressed by general formula (2) and the aminoalkyl (meth)acrylate expressed by general formula (5) uses a dehydration condensation agent:

5. A (meth)acrylic copolymer, comprising a repeat unit expressed by general formula (6), the (meth)acrylic copolymer being obtained by polymerization of the alicyclic ester compound produced by the method according to claim 1 :

where R 1 through R 4 are the same as those in general formula (1).

6. The (meth)acrylic copolymer according to claim 5 , further comprising at least one type of repeat unit expressed by general formula (7) or (8) and at least one type of repeat unit expressed by general formula (9) or (10):

where R 5 represents hydrogen or a methyl group, R 6 represents an alkyl group having a carbon number of 1 to 4, and R 7 represents a cycloalkylene group having a carbon number of 5 to 20, or an alicyclic alkylene group;

where R 8 represents hydrogen or a methyl group, R 9 and R 10 may be the same as, or different from, each other and independently represent an alkyl group having a carbon number of 1 to 4, and R 11 represents an alkyl group having a carbon number of 1 to 4, a cycloalkyl group having a carbon number of 5 to 20, or an alicyclic alkyl group;

where R 12 represents hydrogen or a methyl group, Z represents methylene(-CH 2 —) or oxa(-O—), X(s) may be the same as, or different from, each other and independently represent a hydroxyl group, a halogen group, a nitrile group, a carboxylic acid group, an alkyl carboxylate group having a carbon number of 1 to 4, or an alkoxide group having a carbon number of 1 to 4, and I represents 0 to 2;

where R 13 represents hydrogen or a methyl group, m represents 1 to 3, R 14 represents a methyl group, an ethyl group, a hydroxyl group or a halogen group, and n represents 0 to 2.

7. A photosensitive resin composition, comprising the (meth)acrylic copolymer according to claim 5 and a photoacid generator.

8. An alicyclic ester compound expressed by general formula (1):

where R 1 represents a hydrogen atom or a methyl group, R 2 and R 3 may be the same as, or different from, each other and independently represent a hydrogen atom, a hydroxyl group, a cyclic, linear or branched alkyl group having a carbon number of 1 to 10, an aryl group, a cycloalkyl group, an alkoxy group having a carbon number of 1 to 10, an aryloxy group, an acyloxy group having a carbon number of 2 to 6, or a halogen group, and R 4 represents a linear or branched alkylene group having a carbon number of 2 to 5.

9. A (meth)acrylic copolymer, comprising a repeat unit expressed by general formula (6), the (meth)acrylic copolymer being obtained by polymerization of the alicyclic ester compound produced by the method according to claim 3 :

where R 1 through R 4 are the same as those in general formula (1).

10. The (meth)acrylic copolymer according to claim 9 , further comprising at least one type of repeat unit expressed by general formula (7) or (8) and at least one type of repeat unit expressed by general formula (9) or (10):

where R 5 represents hydrogen or a methyl group, R 6 represents an alkyl group having a carbon number of 1 to 4, and R 7 represents a cycloalkylene group having a carbon number of 5 to 20, or an alicyclic alkylene group;

Assignees

• Mitsubishi Gas Chemical Co
• Mitsubishi Gas Chemical Co

Inventors

• Hayakawa Shoichi
• Horikoshi Hiroshi
• Furukawa Kikuo
• Tanaka Hiroyasu
• TANAGI Hiroyuki

Classifications

• C07C235/40 Primary

  having carbon atoms of carboxamide groups bound to carbon atoms of rings other than six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton · CPC title

• C07C231/02

  from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines · CPC title

• C08F20/36

  containing oxygen in addition to the carboxy oxygen {, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate} · CPC title

• C07C2603/74

  Adamantanes · CPC title

• G03F7/0397

  the macromolecular compound having an alicyclic moiety in a side chain · CPC title