JP2007176989A - Antistatic film for fixing electronic member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve problems such as pollution by bleedout of a surfactant or migration of ions, deterioration of transparency of a film and a cost increase by a step of providing an antistatic layer in the conventional antistatic film for fixing an electronic member and to provide an antistatic film for fixing the electronic member having excellent antistatic properties and transparency with slight pollution. <P>SOLUTION: The antistatic film for fixing the electronic member has a pressure-sensitive adhesive layer. Furthermore, the pressure-sensitive adhesive layer is composed of a hydrocarbyl (meth)acrylate copolymer having at least one specific quaternary onium-organic acid salt group in the molecular side chain in at least a part of at least one surface of a film substrate. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic film for fixing an electronic member. More specifically, the present invention relates to an antistatic film for fixing an electronic member used when manufacturing electrical, electronic and semiconductor parts.

Electronic member fixing film is used when polishing or thinning (back-grinding) an electronic member such as a semiconductor wafer, a BGA (Ball Grit Array) substrate, or a CSP (Chip Scale Package) substrate. It is used for fixing at the time of cutting (dicing), and for fixing at the same time that the small chip is picked up (mounted) on a lead frame or the like.
Conventionally, as the electronic member fixing film, a film in which an adhesive layer is laminated on a plastic (polyvinyl chloride, polyester, polyethylene, polypropylene, etc.) film is used.

These fixing films not only adversely affect the electronic member when static electricity is charged, but also have the problem of contaminating the electronic member by adsorbing dust particles and cutting powder generated during dicing. is there. Therefore, the following method has been proposed for the electronic member fixing film in order to prevent static electricity.
(1) An antistatic property is imparted to the base film constituting the film (see, for example, Patent Document 1).
(2) An antistatic agent-containing layer is provided between the base film constituting the film and the pressure-sensitive adhesive layer or on the side having no pressure-sensitive adhesive layer (see, for example, Patent Document 2).
(3) An antistatic property is imparted to the pressure-sensitive adhesive layer constituting the film (see, for example, Patent Document 3).

JP 58-191777 A Japanese Patent Laid-Open No. 7-26223 JP-A-5-166692

However, the methods (1) to (3) have the following problems.
(1) is a method of kneading a low molecular surfactant, a polymer antistatic agent, metal powder, carbon black, etc. into a base film. Contamination of the adherend due to bleed out of the surfactant, There are problems such as a decrease in transparency.
(2) is a method of providing an antistatic agent-containing layer composed of a low molecular surfactant, an antistatic resin, a conductive resin, etc., but contamination of the adherend due to bleed out of the surfactant or movement of ions. Further, there are problems such as a decrease in transparency of the film and an increase in cost due to an increase in the step of providing the antistatic agent-containing layer.
(3) is a method of kneading a low-molecular surfactant, a polymer antistatic agent, metal powder, carbon black, etc. into the adhesive layer. There are problems such as changes over time and reduced transparency of the film.

As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention provides a hydrocarbyl (meth) having at least one quaternary onium / organic acid group represented by the following general formula (1) in a molecular side chain on at least a part of at least one surface of a film substrate. An antistatic film for fixing an electronic member having an adhesive layer made of an acrylate copolymer (A).
[In the formula, Q is N or P, and R ^{1 to} R ³ are each an organic group containing a linear, branched or alicyclic group having 1 to 20 carbon atoms which may contain O and / or N (provided that R any two of the ¹ to R ³ may be bonded to form a heterocyclic ring via O or N if necessary.), R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aromatic ring or alicyclic-containing hydrocarbon group, X ^- represents a residue of a carboxylic acid group, a sulfamic acid group and (sub) polymerizable organic acid selected from the group consisting of phosphoric acid group. ]

The electronic member fixing film of the present invention has the following effects.
(1) Excellent antistatic properties.
(2) Excellent transparency.
(3) Excellent peelability.
(4) Less adherend contamination with ions.
(5) Little change in adhesive strength with time.

  As the film substrate in the present invention, a substrate used for fixing various electronic members can be used without particular limitation. As the base material, it is necessary to prevent damage when processing electronic parts such as back grinding and dicing, and to resist cutting water, for example, polypropylene, polyester, polycarbonate, ethylene / vinyl acetate copolymer. , Ethylene / ethyl acrylate copolymer, ethylene / propylene copolymer, and plastics such as polyvinyl chloride. The film substrate may be a laminate of one kind or two or more kinds of films or a stretched film. The thickness of the film substrate is preferably 500 μm or less, more preferably 10 to 200 μm, and particularly preferably 20 to 50 μm from the viewpoint of easy handling and adhesion to an adherend.

The pressure-sensitive adhesive layer in the present invention comprises a hydrocarbyl (meth) acrylate copolymer (A) having at least one quaternary onium / organic acid group represented by the following general formula (1) in the molecular side chain. .

In the formula, Q represents N or P. R ^{1 to} R ³ each represent a linear, branched, or alicyclic organic group having 1 to 20 (preferably 1 to 12) carbon atoms (hereinafter abbreviated as C) which may contain O and / or N. And any two of R ^{1 to} R ³ may be bonded via O or N as necessary to form a heterocyclic ring.
Examples of the linear, branched or alicyclic organic group which may contain O and / or N include methyl, ethyl, n-propyl, i-propyl, n-, i- and sec-butyl, n -, I- and t-pentyl, n-octyl, 2-ethylhexyl, cyclohexyl groups and the like. When any one of R ^{1 to} R ³ exceeds 20, the antistatic property of the adhesive is deteriorated.

R ⁴ represents a C1-8 alkyl (methyl, ethyl, butyl, hexyl, 2-ethylhexyl, etc.) group, aromatic ring or alicyclic hydrocarbon (phenyl, toluyl, xylyl, benzyl, etc.) group. When C of R ⁴ exceeds 8, the antistatic property of the adhesive is deteriorated. X ⁻ represents a residue of a polymerizable organic acid selected from the group consisting of a carboxylic acid group, a (phosphorous) phosphoric acid group, a sulfonic acid group, and a sulfamic acid group. Examples of the polymerizable organic acid include those described below.

In the production method (A), the organic acid group in the hydrocarbyl (meth) acrylate copolymer (A1) having an organic acid group in the molecular side chain is represented by a fourth formula represented by the following general formula (3). A method of reacting a class onium salt is included.
In formula, Q, R < ¹ > -R < ³ > and R < ⁴ > represent the same thing as the said Formula (1).
Z ⁻ represents a counter anion selected from the group consisting of residues of alkylating agents and hydroxyl ions. Examples of the alkylating agent include those described below.

  Hydrocarbyl (meth) acrylate copolymer (A1) includes hydrocarbyl (meth) acrylate (a1) having a hydrocarbyl group C of 4 to 18, monomer (a2) containing an organic acid group, and necessary Thus, a copolymer having the other polymerizable monomer (a3) as a structural unit is included.

The hydrocarbyl group of (a1) is an aliphatic group [C1-25 (preferably 4-18), such as alkyl [methyl, ethyl, n- and i-propyl, n-, i-, sec- and t. -Butyl, n-, i-, sec- and neopentyl, n-octyl, 2-ethylhexyl, nonyl, decyl, lauryl, tridecyl, myristyl, cetyl and stearyl etc.] groups and alkenyl [ethenyl, propenyl, butenyl, hexenyl, decenyl And oleyl groups], alicyclic groups [C4-18, such as cyclobutyl, cyclopentyl and cyclohexyl groups] and araliphatic groups [C7-18, such as benzyl and phenylethyl groups] carbyl groups, and two of these The above mixture is mentioned.
Among these, from the viewpoint of the glass transition point (A) (hereinafter abbreviated as Tg, measurement is based on DSC (scanning differential thermal analysis) method), an aliphatic group is preferable, and n-butyl and 2- An ethylhexyl group.

  The monomer (a2) containing an organic acid group includes the following (a21) to (a) which are monomers having an organic acid group [for example, a carboxylic acid group, a (phosphite) phosphoric acid group, a sulfonic acid group, a sulfamic acid group]. a24).

(A21) α, β-unsaturated carboxylic acid monobasic acid [C3-10, such as (meth) acrylic acid, crotonic acid, cinnamic acid and vinylbenzoic acid];
Dibasic acids [C4-8, such as maleic acid, itaconic acid, fumaric acid, citraconic acid and mesaconic acid];
Monoester of dibasic acid [monohydrocarbyl (C1-18) ester of dibasic acid];
Succinic acid monoester of hydroxyl group-containing (meth) acrylate represented by the following general formula

_{CH 2 = C (R ')} - COO (AO) n (CO-L-O) m -CO-CH 2 -CH 2 -COOH

(In the formula, A represents a C2-4 alkylene group, n represents an integer of 1-30, L represents a C3-19 alkylene group, m represents an integer of 0-5, and R ′ represents H or a methyl group.)
[C8-130, for example 2-hydroxyalkyl (alkyl group is C2-3) (meth) acrylate succinic anhydride ring-opening adduct, (poly) (n = 1-30) oxyalkylene (C2-4) mono ( Succinic anhydride ring-opening adduct of meth) acrylate, compound obtained by ring-opening addition of succinic anhydride to caprolactone (1-5 mol) adduct of 2-hydroxyalkyl (alkyl group C2-3) (meth) acrylate, etc. ];
And mixtures of two or more of these

(A22) α, β-unsaturated (phosphite) phosphate monomer (meth) acryloyloxyethyl acid phosphate, (meth) acryloyloxypropyl acid phosphate, (meth) acryloyloxy-2-hydroxypropyl acid phosphate, (meth) Acryloyloxy-3-hydroxypropyl acid phosphate, (meth) acryloyloxy-3-chloro-2-hydroxypropyl acid phosphate, allyl alcohol acid phosphate, (meth) acryloyloxyethyl acid phosphate, and mixtures of two or more thereof

(A23) α, β-unsaturated sulfonic acid monomer Vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, isethionic acid (meth) acrylate, and mixtures of two or more thereof

(A24) α, β-unsaturated sulfamic acid monomer N-hydroxyethyl-N- [2- (meth) acryloyloxyethyl] sulfamic acid, N, N-bis [2- (meth) acryloyloxyethyl] sulfamic acid, Adducts of (meth) acryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid, and mixtures of two or more thereof

  Among these, (meth) acrylic acid, maleic acid, itaconic acid, (meth) acryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid, isethionic acid (meth) acrylate, N-hydroxyethyl -N- [2- (meth) acryloyloxyethyl] sulfamic acid and an adduct of (meth) acryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid, more preferably (meth) acrylic acid, (Meth) acryloyloxyethyl acid phosphate, 2-acrylamido-2-methylpropanesulfonic acid and N-hydroxyethyl-N- [2- (meth) acryloyloxyethyl] sulfamic acid, and mixtures of two or more thereof .

  The other polymerizable monomer (a3) includes a monomer (a31) having a reactive functional group and a monomer (a32) having no reactive functional group.

  Examples of (a31) having a reactive functional group include the following (a311) to (a313).

(A311) Hydroxyl-containing compound / unsaturated carboxylic acid ester of C5-12 (1) Hydroxyalkyl (C2-6) (meth) acrylate [hydroxyethyl-, hydroxypropyl- and hydroxybutyl (meth) acrylate etc.], and Lactone (C4-20, for example, butyrolactone, valerolactone, caprolactone and laurolactone) 1-5 mol adduct (2) poly (n = 2-30) oxyalkylene (C2-4) (meth) acrylate [poly (n = 10) Oxyethylene mono (meth) acrylate, etc.]
(3) Poly (n = 2-30) oxyalkylene (C2-4) unsaturated carboxylic acid diester [poly (n = 10) oxyethylenemaleic acid diester, etc.], poly (n = 2-30) oxyalkylene (C2 -4) (meth) allyl ether [poly (n = 10) oxyethylene (meth) allyl ether, etc.]
C3-8 unsaturated alcohol [(meth) allyl alcohol, crotyl alcohol, 1-buten-3-ol, 2-butene-1,4-diol, etc.]
-C8-15 styrene compound [hydroxystyrene, etc.]
C5-20 ethers [hydroxyalkyl (C2-6) alkenyl (C3-6) ethers such as 2-hydroxyethylpropenyl ether]
(4) Methylol group-containing compound / C4-10 hydroxyl group-containing (meth) acrylamide [N-methylol (meth) acrylamide etc.]

(A312) Amino group-containing compound-C5-15 primary, secondary amino group-containing (meth) acrylate [aminoalkyl (C2-6) (meth) acrylate [aminoethyl (meth) acrylate, etc.], alkyl (C1- 6) Aminoalkyl (C1-6) (meth) acrylate [t-butylaminoethyl methacrylate, etc.]
C5-10 primary and secondary amino group-containing acrylamide [N-aminoalkyl (C2-6) (meth) acrylamide such as N-aminoethyl (meth) acrylamide; (meth) acrylamide alkyl (C2-6) alkyl ( C1-6) amines such as (meth) acrylamidoethylbutylamine]
Alkenylamine compounds [C3-15, such as mono- and di- (meth) allylamine, crotylamine]

(A313) Etherified product of methylol group-containing compound / alkyl (C1-4) etherified product of C4-10 hydroxyl group-containing (meth) acrylamide [N-butoxymethyl (meth) acrylamide etc.]

  Of these (a3), (a311) and (a313) are preferable from the viewpoint of the balance between tackiness of adhesive and cohesive force, and 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl ( Meth) acrylate, N-methylol (meth) acrylamide and N-butoxymethyl (meth) acrylamide.

Examples of (a32) having no reactive functional group include the following (a321) to (a325).
(A321) Carbyl (C1-3) (meth) acrylate formed from C1-3 monool (methanol, ethanol, etc.) and (meth) acrylic acid [methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl ( Meth) acrylate, etc.]

(A322) poly (n = 2-30) oxyalkylene alkyl (C1-18) ether (meth) acrylate [methanol ethylene oxide (hereinafter abbreviated as EO) 10 mol adduct (meth) acrylate, methanol propylene oxide ( Hereinafter abbreviated as PO) (Meth) acrylate etc. of 10 mol adduct]

(A323) Nitrogen-containing vinyl compound (1) C3-20 tertiary or quaternary nitrogen-containing (meth) acrylamide compound / tertiary nitrogen-containing [dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, etc.]
・ Quaternary nitrogen-containing vinyl compounds [quaternized products of the above-mentioned tertiary nitrogen-containing vinyl compounds (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate, etc.)]
-C4-20 amide group-containing vinyl compounds excluding the above (meth) acrylamide compounds, such as (meth) acrylformamide, N-methyl-N-vinylacetone amide, cyclic amides (N-vinyl pyrrolidone, etc.)

(2) Tertiary or quaternary nitrogen-containing (meth) acrylate / tertiary nitrogen-containing [dialkyl (C1-4) aminoalkyl (C1-4) (meth) acrylate [N, N-dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate, etc.], heterocyclic-containing (meth) acrylate [morpholinoethyl (meth) acrylate, etc.], etc.
-Quaternary nitrogen-containing [(meth) acrylate [the quaternized product of the above-mentioned tertiary amino group-containing (meth) acrylate (which is quaternized using the quaternizing agent described above), etc.]]

(3) Heterocycle-containing vinyl compound Pyridine compound (C7-14, such as 2- and 4-vinylpyridine), imidazole compound (C5-12, such as N-vinylimidazole), pyrrole compound (C6-13, such as N-vinyl) (4) Nitrile group-containing vinyl compounds C3-15 nitrile group-containing vinyl compounds such as (meth) acrylonitrile, cyanostyrene, cyanoalkyl (C1-4) acrylates (5) Other vinyl compounds Nitro group-containing vinyl compounds (C8-16, such as nitrostyrene) etc.

(A324) Unsaturated hydrocarbon (1) Aliphatic unsaturated hydrocarbon C2-18 or more olefin [ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, etc.], C4- 10 or more dienes [butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, etc.] and the like (2) alicyclic unsaturated hydrocarbon C4-18 or more cyclic unsaturated Saturated hydrocarbons such as cyclohexene, (di) cyclopentadiene, pinene, limonene, indene (3) Aromatic unsaturated hydrocarbons C8-20 or more aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, vinyl Toluene, 2,4-dimethylstyrene, ethylstyrene, isopropyls Ren, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene

(A325) Vinyl ester, vinyl ether, vinyl ketone, unsaturated dicarboxylic acid diester (1) Vinyl ester / aliphatic vinyl ester (C4-15, such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl adipate, isopropenyl Acetate, vinyl methoxyacetate, vinyl benzoate)
Aromatic vinyl esters (C9-20, such as diallyl phthalate, methyl-4-vinylbenzoate, acetoxystyrene)

(2) Vinyl ether / aliphatic vinyl ether [C3-15, such as vinyl alkyl (C1-10) ether [vinyl methyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, etc.], vinyl alkoxy (C1-6) alkyl (C1-4 ) Ether [vinyl-2-methoxyethyl ether, methoxybutadiene, 3,4-dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, etc.], poly (2-4) (Meth) allyloxyalkane (C2-6) [diallyloxyethane, triaryloxyethane, tetraallyloxybutane, tetrametaallyloxyethane, etc.]
Aromatic vinyl ether (C8-20, such as vinyl phenyl ether, phenoxystyrene)

(3) Vinyl ketone / aliphatic vinyl ketone (C4-25, such as vinyl methyl ketone, vinyl ethyl ketone) / aromatic vinyl ketone (C9-21, such as vinyl phenyl ketone)
(4) Unsaturated dicarboxylic acid diesters C4-34 unsaturated dicarboxylic acid diesters such as dialkyl fumarate (two alkyl groups are C1-22 linear, branched or alicyclic groups), dialkyl Maleate (two alkyl groups are C1-22 linear, branched or alicyclic groups)

  Among those exemplified as (a32) having no reactive functional group, (a321), (a323), (a324) and (a325) are more preferable from the viewpoint of the cohesive strength of the pressure-sensitive adhesive, and (a325) is more preferable. a321), (a323) (1), (2), (a324) (3) and (a325), particularly preferred are methyl (meth) acrylate, ethyl (meth) acrylate, styrene and vinyl acetate.

  The hydrocarbyl (meth) acrylate copolymer (A1) is composed of (a1), (a2) and, if necessary, (a3). The weight ratio [(a1) :( a2) :( a3)] of (a1), (a2) and (a3) is preferably (30 to 99.8) from the viewpoint of tackiness, adhesive strength and cohesive strength of the adhesive. ): (0.2-30): (0-40), more preferably (50-99.5): (0.5-25): (0-30), particularly preferably (65-99): (1-20): (0-20). When the ratio of (a1) is 30 or more, tack and adhesive strength are excellent, and when it is 99.8 or less, cohesion is excellent. When the ratio of (a2) is 0.2 or more, the cohesive force is excellent, and when it is 30 or less, the tack and the adhesive force are excellent. Further, when the ratio of (a3) is 40 or less, tack and adhesive strength are excellent.

  The quaternary onium salt constituting (A) in the present invention includes those obtained by quaternizing a tertiary amine or tertiary phosphine with an alkylating agent.

  Tertiary amines include aliphatic amines (C3-30, such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, diethyl-1-propylamine), aromatic Amines (C6-30, such as triphenylamine, N-ethyl-N-propylaniline), alicyclic amines (C8-30, such as N, N-dimethylcyclohexylamine), heterocyclic amines [C5-30, For example, N-methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N, N′-dimethylpiperazine, 1, 5-Diazabicyclo [4,3,0] nonene-5,1,8-diazabisch [5,4,0] undecene-7, pyridine, 1-methylimidazole, 1,2-dimethylimidazole, 1,2, -dimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, 1,2,4- Trimethylimidazoline etc.] and the like.

  Tertiary phosphine includes aliphatic phosphine (C3-30, such as trimethylphosphine, triethylphosphine), aromatic phosphine (C8-30, such as triphenylphosphine), and alicyclic phosphine (C8-30, such as tricyclohexylphosphine). Etc .;

  Of these, tertiary amines are preferable from an industrial viewpoint, and trimethylamine, triethylamine, tri-n-butylamine, 1,5-diazabicyclo [4,3,0] nonene-5, 1,8 are more preferable. -Diazabicyclo [5,4,0] undecene-7,1,2,4-trimethylimidazoline and mixtures thereof.

  The tertiary amine and tertiary phosphine can also be obtained by tertiaryizing a 1,2 secondary amine or 1,2 secondary phosphine with an alkylating agent.

Examples of the primary and secondary amines include the following.
Primary amines include aliphatic amines (C1-20, such as ethylamine, octylamine, dodecaneamine), aromatic amines (C6-20, such as aniline, naphthylamine), alicyclic amines (C6-20, such as cyclohexylamine). ), And mixtures thereof;
Secondary amines include aliphatic amines (C2-20, such as dimethylamine, diethylamine), aromatic amines (C7-20, such as N-methylaniline, diphenylamine, phenylnaphthylamine), alicyclic amines (C7-20, For example, N-methylcyclohexylamine), heterocyclic amines (C5-20, such as N-methyl-2-furylamine), and mixtures thereof.

Examples of the primary and secondary phosphine include the following.
Primary phosphine includes aliphatic phosphine (C1-20, such as methylphosphine, ethylphosphine), aromatic phosphine (C6-14, such as phenylphosphine, naphthylphosphine), alicyclic phosphine (C6-14, such as cyclohexylphosphine). ), And mixtures thereof;
Secondary phosphines include aliphatic phosphines (C2-20, such as dimethylphosphine, diethylphosphine), aromatic phosphines (C7-20, such as methylphenylphosphine), and alicyclic phosphines (C7-14, such as methylcyclohexylphosphine). And mixtures thereof.

  Examples of alkylating agents include halogenated hydrocarbons [halogenated alkyls (C1-8, such as methyl chloride, ethyl chloride, butyl bromide, methyl iodide), aromatic ring-containing halides (C6-8, such as phenyl bromide, benzyl chloride). Etc.], carbonic acid dialkyl ester (alkyl group is C3-8, such as dimethyl carbonate, diethyl carbonate), dialkyl sulfate ester (C2-8, such as dimethyl sulfate, diethyl sulfate), organic lithium compound (C4-8, such as butyllithium, Phenyl lithium), Grignard reagents (such as those obtained by reacting the above halogenated hydrocarbons with magnesium), and the like.

Among the quaternary onium salts, a quaternary onium / carbonate ester (A2) represented by the following general formula (2) is preferable from the viewpoint of less adherend adherend contamination.

In formula, Q, R < ¹ > -R < ³ > and R < ⁴ > are the same as said Formula (1), R < ⁵ > represents a C1-C8 alkyl group or an aromatic ring containing hydrocarbon group. When C of R ⁵ exceeds 8, the adhesive strength is lowered.

  (A2) is obtained by quaternizing a tertiary amine or tertiary phosphine with the above dialkyl carbonate, and the cation constituting (A2) is the same as the cation in the formula (1).

The following method is mentioned as a manufacturing method of (A2) in this invention.
(1) When a tertiary amine or tertiary phosphine is used A process for producing a tertiary amine or tertiary phosphine and a carbonic acid dialkyl ester (each alkyl group is C1-8, for example, dimethyl carbonate).
(2) In the case of using a 1,2 secondary amine or 1, 2 phosphine After the tertiary amine or phosphine is tertiaryized using the above alkylating agent, it is produced in the same manner as the tertiary amine or tertiary phosphine. Method.

  The equivalent ratio of the tertiary amine or tertiary phosphine to the carbonic acid dialkyl ester in the production method of (A2) is usually 1: (0.3-4), preferably 1: from the industrial viewpoint and the antistatic property. (0.5 to 2), more preferably 1: (1 to 1.5), and particularly preferably 1: (1 to 1.1). If necessary, a solvent [methanol, ethanol, etc.] may be used in the reaction. The reaction temperature is usually 30 to 150 ° C., and preferably 50 to 100 ° C. from an industrial viewpoint.

  The reaction between the quaternary onium salt and the organic acid group in (A1) is carried out in the presence or absence of a solvent, and an anion exchange reaction or neutralization reaction is carried out, whereby a quaternary onium / organic acid is obtained. A hydrocarbyl (meth) acrylate copolymer (A) having a base is obtained.

  When the quaternary onium salt is (A2), the reaction with the organic acid group in (A1) is similarly performed in the presence or absence of a solvent, and carbon dioxide gas by-produced in the anion exchange reaction is generated. By appropriately removing it from the reaction system, a hydrocarbyl (meth) acrylate copolymer (A) having a quaternary onium / organic acid group can be obtained.

  In the production of (A), the equivalent ratio of the quaternary onium salt to the organic acid group in (A1) is usually (0.001 to 1): 1, preferably from the viewpoint of antistatic properties (0.01 -1): 1, more preferably (0.05-1): 1.

  In addition to the method of reacting the organic acid group in (A1) with the quaternary onium salt, (A) is, for example, a polymerizable monomer (a2) containing an organic acid group in advance. At least one organic acid group and a quaternary onium salt are reacted in the same manner as described above to produce a monomer (a4) having a quaternary onium / organic acid group, It can also be produced by a method of copolymerizing with a1), (a2) and (a3) if necessary.

In the above (a4), when all of R ^{1 to} R ⁴ in the quaternary onium salt represented by the general formula (3) are the same, the crystallinity of the resulting monomer increases, and other monomers In some cases, the solubility in a solvent or a solvent is lowered, making it difficult to handle during polymerization. Therefore, at least one of R ^{1 to} R ⁴ is preferably different in carbon number.

  In the present invention, the content of the quaternary onium / organic acid base represented by the general formula (1) in (A) is based on the weight of (A), and the antistatic property, tack, and adhesion of the adhesive. From the viewpoint of force, it is preferably 0.1 to 30%, more preferably 0.2 to 20%, particularly preferably 0.5 to 10%.

  Weight average molecular weight of (A) [Hereinafter abbreviated as Mw, measurement is based on gel permeation chromatography (GPC) method (polystyrene conversion). In the following, the preferable lower limit is 50,000, more preferably 100,000, particularly preferably 200,000 from the viewpoint of the cohesive strength of the pressure-sensitive adhesive, and the preferable upper limit is 2,000,000 from the viewpoint of the viscosity of the coating liquid. More preferably 1,800,000, particularly preferably 1,200,000.

The lower limit of Tg of (A) is preferably −100 ° C., more preferably −90 ° C., particularly preferably −80 ° C. from the viewpoint of the adhesive strength of the adhesive, and the upper limit preferable from the viewpoint of tack of the adhesive is 30 ° C. More preferably, it is 0 ° C., particularly preferably −10 ° C.
Furthermore, (A) may be used as a mixture of two or more kinds from the viewpoint of the adhesive strength of the pressure-sensitive adhesive.

(A) can be produced by various polymerization methods (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.).
Solvents used in solution polymerization include esters (C2-8, such as ethyl acetate, butyl acetate), alcohols (C1-8, such as methanol, ethanol, octanol), hydrocarbons (C4-8, such as n-butane, cyclohexane). , Toluene), ketone (C3-9, such as methyl ethyl ketone), and the like.
The amount of the solvent used is usually 5 to 900%, preferably 10 to 400% based on the total weight of the monomers, and the monomer concentration (% by weight) is usually 10 to 95%, preferably 20 to 90%. is there.
Examples of the dispersion medium in emulsion polymerization and suspension polymerization include water, alcohol (C1-12, such as ethanol, butanol, 2-ethylhexanol), ester (C4-10, such as ethyl acetate, ethyl propionate), and light naphtha. Can be mentioned.
As an emulsifier in emulsion polymerization, an anionic surfactant [metal soap (sodium oleate, sodium stearate, etc.), sulfate ester (sodium lauryl sulfate, etc.)], nonionic surfactant [polyethylene glycol type surfactant (nonylphenol ethylene) Oxide 40 mol adducts, etc.), polyhydric alcohol type surfactants (ethoxylated tetramethyldecynediol, lauric acid monoglyceride, etc.), etc.] vinyl polymerizable emulsifiers [anion compounds (sulfoethyl sodium methacrylate, etc.), cationic compounds ( Dimethylaminomethyl methacrylate and the like)] and the like.
As a dispersion stabilizer in suspension polymerization, water-soluble polymers [for example, polyvinyl alcohol (polymerization degree 200 to 5,000), polyvinyl pyrrolidone (Mw 2,000 to 1,000,000), etc.]] and water-insoluble are hardly used. Inorganic compounds (for example, hydroxyapatite, magnesium phosphate, barium sulfate, etc.) can be mentioned.
The amount of the dispersion medium used in the emulsion polymerization and suspension polymerization is usually 0.01 to 15%, preferably 0.1 to 10%, based on the total weight of the monomers, and the monomer concentration (% by weight) is usually It is 10 to 90%, preferably 30 to 70%.
The usage-amount of an emulsifier is 0.01 to 15% normally based on the total weight of a monomer, Preferably it is 0.5 to 10%.
Moreover, the usage-amount of a dispersion stabilizer is 0.01-15% normally based on the total weight of a monomer, Preferably it is 0.1-10%.

The above polymerization may be carried out by various polymerization initiators [azo compounds [2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile, etc.)], peroxides (benzoylperoxide). Oxide, di-t-butyl peroxide, lauryl peroxide, etc.).
Further, the system temperature in the polymerization reaction is usually −5 to 150 ° C., preferably 30 to 120 ° C. from the viewpoint of easy temperature control, and the reaction time is usually 0.1 to 50 hours, preferably from the viewpoint of easy production. Is 2 to 24 hours. The end point of the reaction can be confirmed by measuring with a gas chromatography or the like that the monomer residual ratio (% by weight) is usually 5% or less, preferably 1% or less.

  In order to further improve the cohesive force of (A) of the present invention, a reactive functional group (A) that reacts with a functional group having active hydrogen (such as a carboxyl group, a hydroxyl group, an amino group, and a methylol group) ( You may further add the crosslinking agent (B) which has 2-5 at least 1 type of functional groups chosen from the group which consists of an isocyanate, an epoxy, a hydrazide, aziridinyl, and an oxazolinyl group in 1 molecule.

  The molecular weight per functional group of (B) is preferably a lower limit of 40, more preferably 60 from the viewpoint of cohesive force and adhesive force and tack of the pressure-sensitive adhesive, and a preferable upper limit from the viewpoint of cohesive force and adhesive force is the number average molecular weight [ Hereinafter, abbreviated as Mn and measurement is based on a titration method (end group determination method). ] 20,000, more preferably 10,000, and particularly preferably Mn5,000.

  (B) includes poly (2-8) isocyanate (B1), poly (2-8) epoxide (B2), hydrazide (B3), oxazoline compound (B4) and aziridine compound (B5).

  As the polyisocyanate (B1), C (excluding carbon in the NCO group, the same shall apply hereinafter) 2 to 18 aliphatic polyisocyanate, C4 to 15 alicyclic polyisocyanate, C6 to 20 aromatic polyisocyanate, C8 -15 aliphatic aliphatic polyisocyanates and one or more compounds selected from the group consisting of modified products of these polyisocyanates.

Aliphatic polyisocyanates include diisocyanates [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcapro. Acid, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, etc.], triisocyanate [1,6,11- Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate and lysine ester triisocyanate Phosgenates of reaction products of alkanolamine and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2,6-diisocyanatohexa Noate, etc.], and modified products of the diisocyanate described later.
Among these, tetramethylene diisocyanate and HDI are preferable from the viewpoint of availability and industrial viewpoint.

Examples of alicyclic polyisocyanates include diisocyanates [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4- Cyclohexene-1,2-dicarboxylate, norbornane diisocyanate and the like], triisocyanate [bicycloheptane triisocyanate and the like], and modified products of the diisocyanate described later.
Among these, IPDI, hydrogenated MDI, and hydrogenated TDI are preferable from the viewpoint of availability and industrial viewpoint.

Aromatic polyisocyanates include diisocyanates [tolylene diisocyanate (TDI) [2,4- and 2,6-TDI and mixtures thereof], diphenylmethane diisocyanate (MDI) [4,4′- and 2,4′-MDI. And mixtures thereof], naphthylene diisocyanate (NDI), etc.] mixtures of bifunctional and trifunctional or higher polyisocyanates [crude TDI, crude MDI (polymethylene polyphenylene polyisocyanate), etc.], and modifications of the diisocyanates described below. Thing etc. are mentioned.
Among these, TDI, MDI and NDI are preferable from the viewpoint of availability and industrial viewpoint.

Examples of the araliphatic polyisocyanate include diisocyanates [xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), diisocyanatoethylbenzene, etc.], and modified products of the diisocyanate described later. Etc.
Among these, XDI and TMXDI are preferable from the viewpoint of availability and industrial viewpoint.

  Examples of the modified polyisocyanate include compounds in which a part of the NCO group of the polyisocyanate exemplified above is modified to carbodiimide, uretdione, uretoimine, urea, burette, isocyanurate and / or urethane group.

Among the modified polyisocyanates, the urethane group-modified products include NCO-terminated urethane prepolymers (including free polyisocyanates) obtained by reacting an excess amount of the polyisocyanates exemplified above with active hydrogen compounds. A pseudo-prepolymer).
Examples of the active hydrogen compound include low-molecular polyvalent (divalent to tetravalent or higher) alcohol, and divalent poly (n = 2 to 30) oxyalkylene (C2 to 4).

Examples of the low molecular weight polyvalent (divalent to tetravalent or higher) alcohol include 2- to 3-valent alcohol [aliphatic alcohol [divalent [C2-20, such as ethylene glycol, diethylene glycol, propylene glycol, 1,3- and 1 , 4-butanediol, 1,6-hexanediol, 3-methylpentanediol, neopentyl glycol (hereinafter abbreviated as EG, DEG, PG, BD, HD, MPD, NPG), 1,9-nonanediol, 1, 4-bis (hydroxymethyl) cyclohexane], trivalent [C3-8, such as glycerin, trimethylolpropane (hereinafter abbreviated as GR, TMP), etc.]; alicyclic alcohol [C4-20, such as 1,4-dihydroxycyclohexane (Hereinafter abbreviated as CHD), 2,2-bis (4,4′-hydroxycyclohexyl) pro Bread]; aromatic ring-containing alcohols [C8-15, such as m- and p-xylylene glycol, 1,4-bis (hydroxyethyl) benzene] and the like] and tetrahydric or higher polyhydric alcohols [C5-10 or Further, for example, pentaerythritol, α-methylglucoside, sorbitol (hereinafter abbreviated as PE, MG, SO), xylit, mannitol, glucose, fructose, sucrose, dipentaerythritol (hereinafter abbreviated as DPE), polyglycerin (polymerization) Degree 2-20) etc.].
As the bivalent to trivalent poly (n = 2 to 30) oxyalkylene (C2 to 4), the above low molecular polyhydric alcohol and / or polyhydric phenol (C6 to 20, for example, catechol, resorcinol, bisphenol A, -S, And polyether polyols obtained by adding alkylene oxide (C2-4, hereinafter abbreviated as AO) to -F,).

  The polyisocyanate exemplified above may be blocked with a blocking agent. Examples of the blocking agent include phenol compounds (C6-24, such as phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, chlorophenol, nitrophenol, thymol, mono-, di- and tri-α-phenylethylphenol. Active methylene compounds [C4-20, such as acetoacetate (ethyl acetoacetate, butyl acetoacetate, etc.), malonic acid diesters (diethyl malonate, ethylbutyl malonate, ethylbenzyl malonate, etc.), acetylacetone, Benzimidazole and 1-phenyl-3-methyl-5-pyrazolone]; lactams (C4-12, eg ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolacta Oxime (C3-12, eg acetooxime, methyl ethyl ketone oxime, cyclohexanone oxime, maldooxime, acetoaldoxime, benzophenone oxime and diethylglyoxime); alcohol (C1-24, eg methanol, ethanol, n-butanol, t- Butyl alcohol, t-amyl alcohol, dimethylethynyl carbinol, dimethyl phenyl carbinol, methyl diphenyl carbinol, triphenyl carbinol, 1-nitro-t-butyl carbinol, 1-chloro-t-butyl carbinol and triphenyl Secondary aromatic amines (C6-20, such as diphenylamine, o-, m-, p-ditoluylamine, N-naphthyltoluidine, N-naphthylxylidine, phenol) Α-naphthylamine, phenyl β-naphthylamine, carbazole, 2,2′-dinitrodiphenylamine and 2,2′-dichlorophenylamine); mercapto compounds (C1-18, such as 2-mercaptobenzothiazole, 2-mercaptothiazoline, dodecyl mercaptan) , Ethyl 2-mercaptothiazole, 2-mercapto5-chlorobenzothiazole, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, phenyl mercaptan, toluyl mercaptan, ethylphenyl mercaptan and ethynyldimethylthiocarbinol); imidazole compound (C3- 10, eg imidazole and 2-ethylimidazole); acid amides (C3-50, eg acetanilide, acrylamide and Fine dimer acid amides); imide (C4～10, e.g. succinimide, phthalimide, and glutaric acid imide) and bisulfite salts.

  In the NCO-terminated urethane prepolymer, the equivalent ratio of NCO groups to active hydrogen in the polyisocyanate (NCO / active hydrogen equivalent ratio) is usually 1.1 / 1 to 100/1, preferably 2/1 to 80/1. More preferably, it is 3/1 to 60/1. The NCO content in the urethane prepolymer is usually 3 to 35% by weight.

Examples of the polyepoxide (B2) include glycidyl type polyepoxide (B21) (epoxy equivalent of 80 to 2,500) and non-glycidyl type polyepoxide (B22) (epoxy equivalent of 43 to 10,000).
(B21) includes glycidyl ether [polyglycol (above) glycidyl ether (bisphenol A di-, bisphenol F di- and pyrogallol triglycidyl ether, etc.), low molecular polyhydric alcohol (above) glycidyl ether (ethylene glycol) , Propylene glycol and neopentyl glycol diglycidyl ether, trimethylolpropane and glycerin triglycidyl ether, etc.), glycidyl ether of polyether polyol (described above) [polyethylene glycol (Mw 200 to 2,000), polypropylene glycol (Mw 200 to 2,000) ) And diglycidyl ether of AO 1-20 mol adduct of bisphenol A]]; glycidyl ester [polycarboxylic acid (n = 2 to 4 or more) Glycidyl ester (adipic acid, phthalic acid and dimer acid diglycidyl ester, trimellitic acid triglycidyl ester, etc.); glycidyl amine [primary amine (above) or glycidylated poly (n = 2-4 or more) amine [N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidylxylylenediamine, 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidylhexamethylenediamine] and the like.

  (B22) include aliphatic polyepoxides [C4-20, such as epoxidized (poly) alkadiene [epoxidized butadiene, epoxidized poly (n = 2 to 4 or more) butadiene, epoxidized oil (epoxidized soybean oil, etc.] And the like] and alicyclic polyepoxides (such as limonene dioxide and dicyclopentadiene dioxide).

  As the hydrazide (B3), polycarboxylic acids [C2-15, such as aliphatic (oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, maleic acid), aromatic (phthalic acid, terephthalic acid, isophthalic acid, Naphthalenedicarboxylic acid etc.)] and the like, and alkylene (C2-6) dihydrazide (ethylene-1,2- and propylene-1,3-dihydrazide etc.).

  Examples of the oxazoline compound (B4) include C3-10, such as 2-oxazoline, and 2-alkyl (C1-4) substituted products thereof, such as 2-methyl-, 2-ethyl-2-, 2-isopropyl-2- and 2-n-propyl-2-oxazoline is mentioned.

  Examples of the aziridine compound (B5) include C10-50, for example, poly (n = 2-4 or more) amine derivatives [1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridinyl urea. 1,1 ′-(hexamethylene) bis-3,3-aziridinylurea, etc.], poly (2-aziridinylpropionate) of low molecular weight polyhydric alcohol (described above) [ethylenebis- (2-aziridinini Lupropionate), trimethylolpropane-tris- (2-aziridinylpropionate), 2,4,6-triaziridinyl-1,3,5-triazine and the like.

  From the viewpoint of the cohesive strength of the pressure-sensitive adhesive, the amount of the crosslinking agent (B) used is expressed in terms of an equivalent ratio of the active hydrogen in the copolymer (A) and the functional group (B) that reacts with the active hydrogen. The amount is preferably 1 / 0.01 to 1/2, and more preferably 1 / 0.02 to 1/1.

  When the electronic member fixing film is thinned by polishing the electronic member, the electronic member is firmly bonded to the support plate, while the thinned electronic member obtained after the polishing step is contaminated, It must be peeled off from the support plate without being damaged. Also, when cutting (dicing) into small chips, the adhesive force is reduced and the electronic member is prevented from moving. On the other hand, the pick-up process for collecting the small chips reduces the adhesive strength so that it can be picked up more easily. Is required. As described above, in the method of making it possible to peel easily without sticking residue on the adherend when peeling, active energy rays (ultraviolet rays, X And a method of facilitating peeling by reducing the adhesive force by curing the pressure-sensitive adhesive layer with a wire, electron beam, etc.) and increasing the elastic modulus of the pressure-sensitive adhesive layer. In this method, in addition to (A), an active energy ray polymerizable compound (C) having two or more unsaturated hydrocarbon groups in one molecule and a polymerization initiator (D) may be further added to (A). Good.

  (C) is not particularly limited as long as it has active energy ray polymerizability, and (C) includes polyfunctional (meth) acrylate (C1) and polyalkadiene (C2).

  Examples of (C1) include esterified products of polyvalent hydroxy compound (C11) and unsaturated carboxylic acid (C12), urethanized products of polyvalent hydroxy compound (C11) and (meth) acryloyloxyalkyl isocyanate (C13), and the like. Can be mentioned.

  Examples of (C11) include those exemplified as the active hydrogen compound constituting the (B), acrylic polyol (C111), polyurethane polyol (C112), polyester polyol (C113), polybutadiene polyol (C114) and epoxy polyol (C115). Etc.

As the acrylic polyol (C111), a (co) polymer of a (meth) acrylate monomer containing a hydroxyl group can be used.
As the (meth) acrylate monomer containing a hydroxyl group, (meth) acrylate among those exemplified as the hydroxyl group-containing compound (a311) can be used. Moreover, when polymerizing these monomers, you may copolymerize the (meth) acrylate monomer which does not contain a hydroxyl group arbitrarily. As the (meth) acrylate monomer, the hydrocarbyl (meth) acrylate (a1) constituting (A) can be used.

  As polyurethane polyol (C112), what consists of the said polyisocyanate (B1) and active hydrogen compound which comprise the said (B) can be used.

As the polyester polyol (C113), those composed of at least one polyester-forming monomer (c113-1) selected from the group consisting of the following (1) to (3) can be used.
(1) Carbonic acid or dicarboxylic acid (c113-1), their ester-forming derivatives (c113-2), diol (c113-3) and phenol (c113-4)
(2) Lactone (c113-5)
(3) Hydroxycarboxylic acid (c113-6)

Examples of the dicarboxylic acid in (c113-1) include C2-50 dicarboxylic acids such as the following aliphatic, aromatic ring-containing dicarboxylic acids, alicyclic ring-containing dicarboxylic acids, and other dicarboxylic acids.
(I) Aliphatic dicarboxylic acid Saturated dicarboxylic acid (oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberin Acids, azelaic acid, sebacic acid, decanediic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid), unsaturated dicarboxylic acids (maleic acid, fumaric acid, citraconic acid) , Mesaconic acid, etc.);
(Ii) Aromatic ring-containing dicarboxylic acid terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, phenyl-2,2′- And 4,4′-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate, etc .;
(Iii) Alicyclic ring-containing dicarboxylic acid 1,3- and 1,2-cyclopentanedicarboxylic acid, 1,2-, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,2-, 1,3- and 1,4-cyclohexanediacetic acid and dicyclohexyl-4,4′-dicarboxylic acid, etc .;
(Iv) Other dicarboxylic acids Dimer acids [dimers of unsaturated fatty acids (C8-24, for example, oleic acid, linoleic acid, linolenic acid)] and carboxyalkylated products thereof.

Examples of the ester-forming derivative (c113-2) include esters, acid anhydrides and acid halides of the above dicarboxylic acids, such as carbonic acid or dialkyl (C1-4) esters of the above dicarboxylic acids (dimethyl esters, diethyl esters, dibutyl esters). Etc.) and diphenyl esters, and acid anhydrides (phthalic anhydride, etc.).
The carbonic acid, dicarboxylic acid and their ester-forming derivatives may be used alone or in combination of two or more.
Of these, preferred from the viewpoint of compatibility with (A) are adipic acid, sebacic acid and icosane diacid for aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, phthalic acid and 5 for aromatic ring-containing dicarboxylic acids. -Sodium sulfoisophthalate; 1,4-cyclohexanedicarboxylic acid for alicyclic dicarboxylic acids; dimethyl carbonate, diphenyl carbonate, dimethyl adipate, dimethyl terephthalate, dimethyl isophthalate, 1,4-cyclohexane for ester-forming derivatives Dicarboxylic acid dimethyl, 5-sulfoisophthalic acid sodium salt dimethyl ester and 5-sulfoisophthalic acid sodium salt diethyl ester, more preferably adipic acid, terephthalic acid, isophthalic acid, phthalic acid, sodium 5-sulfoisophthalate, dicarbonate Chill, terephthalic acid dimethyl, dimethyl isophthalate and 5-sulfoisophthalic acid sodium salt, dimethyl ester.

Examples of the diol (c113-3) include a dihydric alcohol (C2-20), a polyoxyalkylene (Mn200 to 10,000), and an AO adduct of the dihydric alcohol or phenol compound.
Examples of the dihydric alcohol include aliphatic (C2-20), alicyclic (C5-12), and araliphatic glycol (C8-26). Specific examples of these dihydric alcohols include the above-mentioned dihydric alcohol. Aliphatic, alicyclic and aromatic ring-containing dihydric alcohols among the low molecular weight polyhydric alcohols can be mentioned.
The diol (c113-3) may be used alone or in combination of two or more.
Among these, EG, PG, BD (especially 1,4-BD), NPG, HD (especially 1,6-HD), CHD, polyethylene glycol (hereinafter abbreviated as PEG) are preferable from the viewpoint of easy handling. , Polypropylene glycol (hereinafter abbreviated as PPG), polytetramethylene glycol (hereinafter abbreviated as PTMG), an EO adduct of bisphenol A and a PO adduct of bisphenol A, more preferably EG, 1,4-BD, 1,6 -HD, PEG, PTMG, EO addition of bisphenol A and PO addition of bisphenol A.
The molecular weight of the diol is preferably 10,000 or less, more preferably 4,000 or less, and particularly preferably 62 to 3,000, from the viewpoint of easy coating.

  Phenol (c113-4) includes monocyclic polyhydric phenol [C6-30, such as divalent (catechol, resorcinol, hydroquinone, urushiol), trivalent (C6-15, such as pyrogallol), tetravalent (C6-15). , Eg 1,2,4,5-tetrahydroxybenzene)]; condensed polycyclic dihydric phenol [C10-30, eg dihydroxynaphthalene, binaphthol]; bisphenol [C13-30, eg bisphenol A, -F, -C, -B, -AD and -S]; dihydroxybiphenyl, 4,4'-dihydroxydiphenyl-2,2-butane and the like.

Lactone (c113-5) includes C4-20 lactones such as γ-butyrolactone, γ- and δ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, lauro. Examples include lactone, undecanolactone, eicosanolactone, and a mixture of two or more thereof.
Of these, γ-butyrolactone, ε-caprolactone, δ-valerolactone, enanthlactone and laurolactone are preferred from the viewpoint of ease of handling.
Hydroxycarboxylic acid (c113-6) includes C2-20 hydroxycarboxylic acids such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, ω-hydroxycapric acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 20-hydroxyeicosanoic acid and mixtures of two or more thereof.
Among these, ω-hydroxycaproic acid, 11-hydroxyundecanoic acid and 12-hydroxydodecanoic acid are preferable from the viewpoint of easy handling.

The polyester polyol (C113) can be produced by the method described in JP-B-58-19696 using the above polyester-forming monomer.
The lower limit of Mn in (C113) is preferably 500 from the viewpoint of adhesive strength, more preferably 800, and the upper limit preferable from the viewpoint of coatability is 20,000, more preferably 10,000.

  Examples of the polybutadiene polyol (C114) include Mn 500 to 20,000, for example, homopolymers and copolymers of butadiene having a hydroxyl group at the terminal [for example, butadiene / styrene copolymer and butadiene / acrylonitrile copolymer].

  The epoxy polyol (C115) is formed from Mn 500 to 20,000, for example, the polyepoxide (B2) and an active hydrogen compound (the polyhydric alcohol, polyhydric alcohol and / or AO adduct of polyhydric phenol, etc.). And terminal OH polyol containing a plurality of epoxy groups in the molecule.

  As unsaturated carboxylic acid (C12), the unsaturated carboxylic acid illustrated by said (a21) is mentioned, for example.

  Among (C1), when producing an esterified product comprising a polyvalent hydroxy compound (C11) and an unsaturated carboxylic acid (C12), the equivalent ratio in the reaction of (C11) and (C12) is not particularly limited. From the viewpoint of non-contamination to the adherend, it is preferably 1/10 to 10/1, more preferably 1/5 to 2/1.

  (Meth) acryloyloxyalkyl isocyanate (C13) includes (meth) acryloyloxy groups bonded to isocyanate groups via C2-6 alkylene groups, such as 2- (meth) acryloyloxyethyl isocyanate, 4- Examples include (meth) acryloyloxybutyl isocyanate.

  In producing a urethanized product comprising the polyvalent hydroxy compound (C11) and the (meth) acryloyloxyalkyl isocyanate (C13) in (C1), the OH / NCO equivalent ratio in the reaction of (C11) and (C13) Is not particularly limited, but is preferably from 1/10 to 10/1, more preferably from 1/5 to 2/1, from the viewpoint of non-contamination to the adherend.

  Specific examples of the polyfunctional (meth) acrylate (C1) include, for example, TMP tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, PE tri (meth) acrylate, PE tetra (meth) acrylate, DPE monohydroxy Penta (meth) acrylate, DPE hexa (meth) acrylate, 1,4-BD di (meth) acrylate, PEG di (meth) acrylate, polybutadienediol di (meth) acrylate, 2-hydroxyethyl acrylate / n-butyl acrylate Polymer (meth) acryloyl isocyanate adduct, PPG / 4,4′MDI adduct (meth) acryloyl isocyanate adduct, EG / methacryloyl isocyanate adduct of adipic acid polyester and bisphenol A Methacryloyl isocyanate adduct of carboxymethyl product / EG adducts

  The polyalkadiene (C2) is obtained by (co) polymerizing alkadiene (C4-30, such as butadiene or isoprene), and examples thereof include polybutadiene and polyisoprene.

Mn of (C) is preferably 100 to 30,000, more preferably 500 to 20,000, from the viewpoint of adhesive strength before curing.
The amount of (C) used is preferably 10 to 300%, more preferably 40 to 150% from the viewpoint of the adhesive strength before curing, based on the weight of (A).

Moreover, a polymerization initiator (D) can be used for the purpose of increasing the curing rate during curing with active energy rays.
Examples of (D) include α-ketol (D1), acetophenone (D2), benzoin ether (D3), ketal (D4), aromatic sulfonyl chloride (D5), oxime (D6), benzophenone (D7), thioxanthone ( D8), camphorquinone, halogenated ketones (for example, 1,1-dichloro-2-propanone, 1,1,1-trichloro-2-propanone), acylphosphinoxide, acylphosphonate and the like.

(D1) includes 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α′-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, -Hydroxycyclohexyl phenyl ketone and the like;
(D2) includes methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1- [4- (methylthio) -phenyl] -2-morpholinopropane -1 etc .;
(D3) includes benzoin ethyl ether, benzoin isopropyl ether, anisoin methyl ether and the like;
(D4) includes benzyl dimethyl ketal and the like;

(D5) includes naphthalenesulfonyl chloride and the like;
(D6) includes 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime and the like;
(D7) includes benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, etc .;
(D8) includes thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthio Xanthone, 2,4-diisopropylthioxanthone, and the like.

  The amount of (D) used is 0.01 to 50%, preferably 0.05 to 20%, based on the weight of (A).

  In the pressure-sensitive adhesive layer of the present invention, the tackifying resin (E1), the plasticizer (E2), the filler (E3), the pigment (E4), and the ultraviolet ray absorption as required, as long as the effects of the present invention are not impaired. One or more additives (E) selected from the group consisting of the agent (E5) and the antioxidant (E6) can be further contained.

Examples of the tackifier resin (E1) include terpenes, terpene phenols, phenols, aromatic hydrocarbon modified terpenes, rosins, modified rosins, synthetic petroleum (aliphatic, aromatic and alicyclic synthetic petroleum resins, etc.), coumarone- Examples include indene, xylene, styrenic and dicyclopentadiene resins, and hydrogenates of these having unsaturated double bonds, and mixtures thereof.
The amount of (E1) used is usually 100% or less based on the weight of (A), and preferably 5 to 50% from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive layer.

Examples of the plasticizer (E2) include hydrocarbons [C6 or more and Mw 100,000 or less, such as process oil, liquid polybutadiene, liquid polyisobutylene, liquid polyisoprene, liquid paraffin, paraffin wax, ethylene and α-olefin (C3 to 20). (Weight ratio 99.9 / 0.1-0.1 / 99.9) oligomer (Mw 5,000-100,000), α-olefin (C4-20) excluding ethylene and propylene ( Weight ratio 99.9 / 0.1 to 0.1 / 99.9) oligomer (Mw 5,000 to 100,000) etc.]; chlorinated paraffin [chlorinated normal paraffin (C8-22), chlorinated branched paraffin ( C20-32) etc.]; esters [C8-30, such as phthalic acid esters (diethyl phthalate, dibutyl phthalate, Dioctyl phthalate, didecyl phthalate, dilauryl phthalate, distearyl phthalate, diisononyl phthalate, etc.), adipic acid ester (dioctyl adipate, etc.), sebacic acid ester (dioctyl sebacate, etc.), etc .; And hydrogenates of those having an unsaturated double bond; and mixtures thereof.
The amount of (E2) used is usually 50% or less based on the weight of (A), and preferably 2 to 30% from the viewpoint of the adhesive strength and cohesive strength of the pressure-sensitive adhesive layer.

Fillers (E3) include carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (aluminum sulfate, calcium sulfate, barium sulfate, etc.), sulfites (calcium sulfite, etc.), metal sulfides (molybdenum disulfide, etc.) Silicates (aluminum silicate, calcium silicate, etc.), diatomaceous earth, quartzite powder, talc, silica, zeolite, and mixtures thereof. (E3) is preferably fine particles having a volume average particle diameter of 0.01 to 5 μm from the viewpoint of the adhesive strength of the adhesive.
The amount of (E3) used is usually 50% or less based on the weight of (A), and preferably 5 to 30% from the viewpoint of tackiness and cohesive strength of the pressure-sensitive adhesive layer.

Examples of the pigment (E4) include inorganic pigments [earth-based pigments (yellow ocher, tail belt, gypsum, etc.), calcined earth (burnt schenner, etc.), mineral pigments (lapis lazuli, azurite, etc.), oxide pigments (cobalt blue, Titanium white, zinc white, etc.), hydroxide pigments (bilijan, alumina white, etc.), sulfide pigments (cadmium yellow, cadmium red, etc.), silicate pigments (talc, clay, etc.), phosphate pigments (mineral violet, etc.) , Carbonate pigments (calcium carbonate, silver white, etc.), metal powder pigments (aluminum powder, gold powder, etc.), carbon pigments (carbon black, ivory black, etc.), organic pigments (vegetable pigments (madder lake, etc.), animal nature Pigments (cochineal, sepia, etc.), lake pigments (alizarin lake, quinoline yellow Azo pigments (first yellow, disazo yellow, naphthol red, etc.), azo complex pigments (nickel azo yellow, benzimidazolone yellow, etc.), phthalocyanine pigments (phthalocyanine blue, etc.), condensed polycyclic pigments (thioindigo, perylene red) And the like, and mixtures thereof.
(E4) is preferably fine particles having a volume average particle diameter of 0.01 to 5 μm from the viewpoint of the adhesive strength of the pressure-sensitive adhesive layer. The amount of (E4) used is usually 20% or less based on the weight of (A), and preferably 1 to 10% from the viewpoint of tackiness and cohesive strength of the pressure-sensitive adhesive layer.

Antioxidants (E5) include hindered phenols [2,6-di-t-butyl-p-cresol (BHT), 2,2′-methylenebis (4-methyl-6-t-butylphenol), tri Ethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate] etc.]; Sulfur [Dilauryl 3,3′-thiodipropionate (DLTDP), Distearyl 3,3′-thiodipropionate (DSTDP), etc.]]; Phosphorus [may have a halogen Organic phosphites such as triphenyl phosphite (TPP), triisodecyl phosphite (TDP), tris (2,4-di-t-butyl Benzyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and their halo-substituted products]; hindered amine system [octyldiphenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine etc.]; and mixtures thereof.
The amount of (E5) used is usually 5% or less based on the weight of (A), and preferably 0.05 to 1% from the viewpoint of the adhesive strength of the pressure-sensitive adhesive layer.

Examples of the ultraviolet absorber (E6) include salicylic acid derivatives (phenyl salicylate, salicylic acid-p-octylphenyl, salicylic acid-p-tert-butylphenyl, etc.); benzophenone compounds [2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy Benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sulfobenzophenone, 2- Hydroxy-4-methoxy-2′-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2, 2 ', 4 4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane Etc.]; benzotriazole compounds {2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert- Butyl-phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-4′-n-octoxyphenyl) benzotriazole, -(2'-hydroxy-5'-n-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- [2' -Hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2-methylenebis [4- (1,1,3,3- Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like}; cyanoacrylate compounds (2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-cyano-3, 3'-diphenyl acrylate, etc.); and mixtures thereof.
The amount of (E6) used is usually 5% or less based on the weight of (A), preferably 0.1 to 1% from the viewpoint of the adhesive strength of the pressure-sensitive adhesive layer.

  The total use amount of (E) based on the weight of (A) is usually 230% or less, preferably 150% or less, more preferably 10 to 120% from the viewpoint of the adhesive strength and tack of the pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive in the present invention was produced separately from each other (A), and if necessary, (B), (C), (D) and / or (E) were mixed with a normal mixing device (mixing tank with a stirrer, For example, a static mixer). (E) may be added at the stage of production of (A) (raw material before production, reaction product during production or product after production).

The pressure-sensitive adhesive is preferably used as a solution added with a solvent, an emulsion or a dispersion from the viewpoint of coating.
Solvents include esters (C2-8, such as methyl formate, ethyl acetate, butyl acetate), alcohols (C1-8, such as isopropanol), hydrocarbons (C4-8, such as hexane, cyclohexane, toluene, xylene), ketones ( C3-9, such as acetone, methyl ethyl ketone, cyclohexanone) and the like. From the viewpoint of coatability, the amount used is preferably 5 to 900%, more preferably 10 to 400% based on the weight of (A). Yes, the solid concentration of the solution is preferably 10 to 95%, more preferably 20 to 90%.
The viscosity (25 ° C.) of the solution is preferably 100 to 50,000 mPa · s, more preferably 200 to 30,000 mPa · s from the viewpoint of coating.

Examples of the dispersion medium in the emulsion and dispersion, the emulsifier in the emulsion, and the dispersion stabilizer in the dispersion include those exemplified in the emulsion polymerization and suspension polymerization of (A). The amount of the dispersion medium used is preferably 10 to 900%, more preferably 50 to 500%, based on the total solid content of the pressure-sensitive adhesive, from the viewpoint of coating properties.
The use amount of the emulsifier is preferably 0.1 to 10%, more preferably 0.5 to 8% based on the total weight of the solid content of the pressure-sensitive adhesive, from the viewpoint of the adhesive strength and water resistance of the pressure-sensitive adhesive. Is preferably 0.1 to 10%, more preferably 0.5 to 8% based on the total weight of the solid content of the pressure-sensitive adhesive from the viewpoint of the pressure-sensitive adhesive strength of the pressure-sensitive adhesive.
The viscosity (25 ° C.) of the emulsion and dispersion is preferably 10 to 20,000 mPa · s, more preferably 50 to 10,000 mPa · s from the viewpoint of coating.

The film for fixing an electronic member of the present invention has the pressure-sensitive adhesive layer composed of the above (A) on at least one surface of a film substrate. The film is made of an adhesive obtained by mixing (A), and further (B), (C), (D) and / or (E) if necessary, using at least one of the above-mentioned film base materials. Apply directly to one side, heat to dry the solvent or dispersion medium, proceed with the reaction, further cure and cure, or apply to the release film in the same way, then dry and cure The pressure-sensitive adhesive layer obtained in this way can be produced by a method of transferring to at least one side of the substrate.
Examples of the coating apparatus include a gravure coater, a roll coater, a reverse coater, a doctor blade, a bar coater, a comma coater, a fountain die coater, a lip coater, and a knife coater.

Examples of heating means for curing the pressure-sensitive adhesive include hot air (60 to 150 ° C.), (near) infrared rays, and high frequencies.
Moreover, as said curing conditions, about 3 to 7 days at room temperature or about 12 to 72 hours at 45 degreeC is mentioned, for example.
The coating thickness (after drying) of the pressure-sensitive adhesive layer in the present invention is usually 1 to 100 μm, and preferably 5 to 50 μm from the viewpoint of adhesive strength.
Examples of the electronic member that is an object of the antistatic film of the present invention include a semiconductor wafer, a BGA (ball grit array) substrate, and a CSP (chip scale type package) substrate. Examples of the material of the semiconductor wafer include silicon, germanium, gallium-arsenic, gallium-phosphorus, and gallium-arsenic-aluminum.
In addition, the antistatic film of the present invention is irradiated with active energy rays (ultraviolet rays, X-rays, electron beams, etc.) after the polishing process of the electronic member is completed, and the adhesive layer is cured to increase the elastic modulus. The adhesive strength is reduced, and the obtained thinned electronic member or the like can be easily peeled off.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to this. In the following, “parts” represents parts by weight, and “%” represents% by weight.

[Production of quaternary onium carbonate ester salt (A2)]
Production Example 1
A stirred autoclave was charged with 101 parts of triethylamine, 90 parts of dimethyl carbonate and 64 parts of methanol as a solvent, reacted at a reaction temperature of 110 ° C. for 12 hours, and then distilled off methanol at 50 ° C. under reduced pressure to give methyltriethylammonium. -191 parts of monomethyl carbonate (A2-1) were obtained.

[Production of Monomer (a4) Having Quaternary Onium / Organic Acid Base]
Production Example 2
A stirring autoclave was charged with 101 parts of triethylamine, 90 parts of dimethyl carbonate and 64 parts of methanol as a solvent, and reacted at a reaction temperature of 110 ° C. for 12 hours to obtain a 75% methanol solution of methyltriethylammonium monomethyl carbonate (A2-1). It was. This product was charged with 72 parts of acrylic acid, and 187 parts of methyltriethylammonium acrylate (a4-1) was obtained by removing by-product carbon dioxide and methanol.

[Production of Hydrocarbyl (meth) acrylate Copolymer (A) Having Quaternary Onium / Organic Acid Base]
Production Example 3
A four-necked Kolben equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen gas inlet tube was charged with 184 parts of ethyl acetate and 120 parts of cyclohexane and heated to 75 ° C. Subsequently, 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, a monomer obtained by ring-opening addition of succinic anhydride to a polycaprolactone adduct of 2-hydroxyethyl methacrylate [trade name “ FM-1A ", manufactured by Daicel Chemical Industries, Ltd., the same applies below] 20 parts, and 0.3 part of 2,2'-azobisisobutyronitrile (AIBN) were mixed. The monomer mixture was continuously dropped with a dropping funnel over 4 hours while nitrogen gas was passed through the four-necked Kolben to carry out radical polymerization. After the completion of dropping, a solution prepared by dissolving 1.5 parts of AIBN in 80 parts of ethyl acetate was continuously added using a dropping funnel over a period of 4 hours from 2 hours after the completion of dropping. Furthermore, after continuing the polymerization at the boiling point for 4 hours, 216 parts of toluene was added as a diluent solvent to obtain a hydrocarbyl (meth) acrylate copolymer solution (A1-1) having a carboxylic acid group in the molecular side chain. It was.
By adding 3.2 parts of (A2-1) to 100 parts of (A1-1) and removing the by-produced carbon dioxide, the hydrocarbyl (meth) acrylate copolymer having a quaternary ammonium carboxylate group is obtained. A polymer solution (A-1) was obtained. The viscosity of (A-1) (B-type viscometer: 25 ° C., the same applies hereinafter) is 5,800 mPa · s, the solid content concentration is 41.9%, and the Mw (polystyrene conversion, the same applies hereinafter) by the GPC method is about 47. It was ten thousand.

Production Example 4
In Production Example 3, instead of using 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, and 48 parts of vinyl acetate, 142 parts of n-butyl acrylate, 182 parts of 2-ethylhexyl acrylate, and 40 parts of vinyl acetate were used. Was carried out in the same manner as in Production Example 3 to obtain a hydrocarbyl (meth) acrylate copolymer solution (A1-2) having a carboxylic acid group in the molecular side chain.
Next, 2.1 parts of (A2-1) is added to 100 parts of (A1-2), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium carboxylate group A copolymer solution (A-2) was obtained. The viscosity of (A-2) was 5,000 mPa · s, the solid content concentration was 42.1%, and Mw was about 450,000.

Production Example 5
In Production Example 3, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 190 parts of n-butyl acrylate, 190 parts of 2-ethylhexyl acrylate, 2 parts A hydrocarbyl (meth) acrylate copolymer solution (A1-3) having a carboxylic acid group in the molecular side chain was obtained in the same manner as in Production Example 3 except that 4 parts of hydroxyethyl acrylate were used.
Next, 4.2 parts of (A2-1) is added to 100 parts of (A1-3), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium carboxylate group A solution (A-3) of the copolymer was obtained. The viscosity of (A-3) was 4,700 mPa · s, the solid content concentration was 41.7%, and the Mw was about 510,000.

Production Example 6
In Production Example 3, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 324 parts of 2-ethylhexyl acrylate, 12 parts of itaconic acid, 56 of vinyl acetate Except having used the part, it carried out similarly to manufacture example 3, and obtained the solution (A1-4) of the hydrocarbyl (meth) acrylate copolymer which has a carboxylic acid group in a molecular side chain.
Next, 4.2 parts of (A2-1) is added to 100 parts of (A1-4), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium carboxylate group A solution (A-4) of the copolymer was obtained. The viscosity of (A-4) was 5,400 mPa · s, the solid content concentration was 42.3%, and Mw was about 460,000.

Production Example 7
Manufacturing Example 3 except that n-butyl acrylate 238 parts, 2-ethylhexyl acrylate 78 parts, and “FM-1A” 20 parts were used instead of n-butyl acrylate 152 parts and 2-ethylhexyl acrylate 184 parts. It carried out similarly to Example 3 and obtained the solution (A1-5) of the hydrocarbyl (meth) acrylate copolymer which has a carboxylic acid group in a molecular side chain.
Next, 2.4 parts of (A2-1) is added to 100 parts of (A1-5), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium carboxylate group A solution (A-5) of the copolymer was obtained. The viscosity of (A-5) was 4,200 mPa · s, the solid content concentration was 42.1%, and Mw was about 450,000.

Production Example 8
In Production Example 3, 184 parts of ethyl acetate, 120 parts of cyclohexane, 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, 20 parts of “FM-1A”, AIBN 0.3 A solution of 1.5 parts of AIBN in 80 parts of ethyl acetate, instead of 216 parts of toluene, 88 parts of ethyl acetate, 88 parts of cyclohexane, 24 parts of (a4-1), 140 parts of n-butyl acrylate, 2- Manufactured except that 188 parts of ethylhexyl acrylate, 8 parts of acrylic acid, 20 parts of methyl methacrylate, 20 parts of styrene, 0.4 part of AIBN, 0.4 part of AIBN, and 1.5 parts of AIBN were dissolved, and 336 parts of toluene were used. Hydrocarbyl having a quaternary ammonium carboxylate group (meta ) A solution (A-6) of an acrylate copolymer was obtained. The viscosity of (A-6) was 3,900 mPa · s, the solid content concentration was 40.1%, and Mw was about 410,000.

Production Example 9
In Production Example 3, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A”, 166 parts of n-butyl acrylate, 166 parts of 2-ethylhexyl acrylate, 2 parts -Using 20 parts of methacryloyloxyethyl acid phosphate [trade name "JPA-514", manufactured by Johoku Chemical Co., Ltd.], replacing 216 parts of toluene added as a diluent solvent with 184 parts of ethyl acetate and 120 parts of cyclohexane, A solution of a hydrocarbyl (meth) acrylate copolymer having a phosphate group in the molecular side chain (except for the fact that the solvent was previously charged in a four-necked Kolben and heated up, in the same manner as in Production Example 3) A1-7) was obtained.
Next, 1.1 parts of (A2-1) is added to 100 parts of (A1-7), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium phosphate group A solution (A-7) of a copolymer was obtained. The viscosity of (A-7) was 1,000 mPa · s, the solid content concentration was 42.4%, and Mw was about 100,000.

Production Example 10
In Production Example 3, 120 parts of cyclohexane was replaced with 120 parts of methanol, and 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A” were replaced with n-butyl acrylate. 166 parts, 2-ethylhexyl acrylate 166 parts, 2-acrylamido-2-methylpropane sulfonic acid [trade name “TBAS-Q”, manufactured by Nitto Chemical Co., Ltd.] 20 parts were used in the same manner as in Production Example 3. Then, a hydrocarbyl (meth) acrylate copolymer solution (A1-8) having a sulfonic acid group in the molecular side chain was obtained.
Next, to 100 parts of (A1-8), 1.5 parts of (A2-1) is added, and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium sulfonate group A copolymer solution (A-8) was obtained. The viscosity of (A-8) was 6,900 mPa · s, the solid content concentration was 41.8%, and Mw was about 400,000.

Production Example 11
A four-necked colben was charged with 185 parts of N, N-di (2-hydroxyethyl) sulfamic acid and 593 parts of toluene, and reacted at a reaction temperature of 30 ° C. with methacryloyl isocyanate [trade name “MAI”, Nippon Paint Co., Ltd. )] After 222 parts were added dropwise over 1 hour, the mixture was further reacted for 1 hour, and toluene was distilled off at 50 ° C. under reduced pressure to give methacryloyl isocyanate and N, N-di (2-hydroxyethyl) sulfamic acid. The adduct (B-1) was obtained.
In Production Example 3, 120 parts of cyclohexane was replaced with 120 parts of methanol, and 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, and 20 parts of “FM-1A” were replaced with n-butyl acrylate. 166 parts, 2-ethylhexyl acrylate 166 parts, (B-1) 20 parts, 216 parts of toluene added as a diluent solvent is replaced with 184 parts of ethyl acetate and 120 parts of methanol. Except having prepared and heated up, it carried out similarly to manufacture example 3, and obtained the solution (A1-9) of the hydrocarbyl (meth) acrylate copolymer which has a sulfamic acid group in a molecular side chain.
Next, 0.8 parts of (A2-1) is added to 100 parts of (A1-9), and the same procedure as in Production Example 3 is followed. Hydrocarbyl (meth) acrylate having a quaternary ammonium sulfamate group A solution (A-9) of a copolymer was obtained. The viscosity of (A-9) was 2,900 mPa · s, the solid content concentration was 41.3%, and Mw was about 150,000.

Comparative production example 1
In Production Example 3, instead of 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 150 parts of 2-ethylhexyl acrylate and 12 parts of acrylic acid were used. It carried out similarly to manufacture example 3, and obtained the solution (S-1) of the comparative hydrocarbyl (meth) acrylate copolymer.
The viscosity of (S-1) was 2,900 mPa · s, the solid content concentration was 40.3%, and Mw was about 410,000. (S-1) 250 parts of lithium perchlorate 1.5 parts and polyether diol [trade name “SANNICS PP-400”, manufactured by Sanyo Chemical Industries, Ltd.] 30 parts are blended to compare antistatic properties. A pressure-sensitive adhesive solution (Y-1) was obtained.

Comparative production example 2
In Production Example 3, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 260 parts of n-butyl acrylate and 2-ethylhexyl Except having used 128 parts of acrylates and 12 parts of acrylic acid, it carried out similarly to manufacture example 3, and obtained the solution (S-2) of the comparative hydrocarbyl (meth) acrylate copolymer.
The viscosity of (S-2) was 4,100 mPa · s, the solid content concentration was 40.4%, and Mw was about 460,000. (S-2) 750 parts of lithium perchlorate 7.5 parts, polyether triol [trade name “Sanniks GP-4000”, manufactured by Sanyo Chemical Industries Ltd.] 90 parts, comparative antistatic properties A pressure-sensitive adhesive solution (Y-2) was obtained.

Comparative production example 3
In Production Example 3, instead of 238 parts of n-butyl acrylate, 78 parts of 2-ethylhexyl acrylate, 16 parts of acrylic acid, 48 parts of vinyl acetate, and 20 parts of “FM-1A”, 40 parts of n-butyl acrylate, 2-ethylhexyl Except having used 320 parts of acrylates, 20 parts of acrylic acid, and 20 parts of 2-hydroxyethyl acrylate, it carries out similarly to manufacture example 3, and the solution (S-3) of the comparative hydrocarbyl (meth) acrylate copolymer is used. Obtained.
The viscosity of (S-3) was 2,100 mPa · s, the solid content concentration was 40.3%, and Mw was about 400,000. (S-3) 20 parts of carbon black was dispersed in 980 parts to obtain a comparative antistatic pressure-sensitive adhesive solution (Y-3).

Example 1
(A-1) 10% toluene of N, N, N ′, N′-tetraglycidylxylylenediamine [manufactured by Mitsubishi Gas Chemical Industries, Ltd., trade name: “TETRAD-X”] as a crosslinking agent in 100 parts 1 part of the solution was added and mixed uniformly to prepare a blended solution. This compounded solution was coated on one side of a polyester film [trade name: “Lumirror” type T, manufactured by Toray Industries, Inc.] using a bar coater so that the dry film thickness was 25 μm, and at 60 ° C. for 1 minute. Furthermore, each was dried with hot air at 100 ° C. for 1 minute, and further cured at 45 ° C. for 3 days to prepare an electronic member fixing film. The film was evaluated according to the following performance evaluation method. The results are shown in Table 1.
In the above, “Lumirror” was replaced with a release polyester film [“Super Tech SP-PET38” manufactured by Lintec Corporation], and the same composition was applied onto the film. It peeled from and obtained the adhesive film. The film was evaluated according to the following performance evaluation method. The results are shown in Table 1.

Examples 2-9
Using (A-2) to (A-9), the same operation as in Example 1 was performed, test pieces were prepared, and each performance was evaluated. The evaluation results are shown in Table 1.

Comparative Examples 1-3
Using (Y-1) to (Y-3), the same operation as in Example 1 was performed, test pieces were prepared, and each performance was evaluated. The evaluation results are shown in Table 1.

[Performance evaluation method]
The performance evaluation method used in this example is as follows.
(1) Adhesive strength Affixed to the stainless steel plate (SUS304, the same shall apply hereinafter) with the adhesive-coated surface of the electronic member fixing film test piece so that the affixed area is 25 mm wide × 100 mm long [with a 2 kg load roller 1 reciprocation], after 30 minutes of pasting, and after 30 minutes of pasting, heat treated at 60 ° C. for 1 week according to JIS-Z-0237 at normal temperature (23 ° C.) (unit: N / 25 mm).
(2) Antistatic properties (surface resistivity, volume resistivity)
After the pressure-sensitive adhesive film test piece was allowed to stand for 12 hours under the condition of 23 ° C. × 65% RH, volume specific resistance and surface specific resistance were evaluated by the method described in JIS-K6911.

(3) Transparency The pressure-sensitive adhesive film test piece was visually observed to evaluate the presence or absence of cloudiness of the pressure-sensitive adhesive film.
(4) Peelability After affixing a film test piece for fixing an electronic member on a stainless steel plate so that the affixing area is 25 mm wide × 100 mm long [one reciprocation with a 2 kg load roller], and storing at 60 ° C. for 6 hours The test piece was peeled off after 2 hours at room temperature (23 ° C.), and the presence or absence of contamination such as cloudiness or adhesive residue on the surface of the base material was determined with the naked eye according to the following criteria.

○: No fogging or adhesive residue on the substrate surface.
X: Cloudiness or adhesive residue is recognized on the substrate surface.
XX: The pressure-sensitive adhesive layer cohesively breaks down and there is adhesive residue on the entire surface

(5) Dissolution test (dissolution test of alkali metals and halogen ions)
Put 20 ml of ultrapure water in a 100 ml Erlenmeyer flask, immerse 1 g of adhesive film test piece, leave it in an autoclave at 121 ° C. for 24 hours, concentrate it to 1/10, and concentrate it to an atomic absorption photometer. Was used to measure the concentration of metal ions. The halogen ion was measured by a colorimetric method.
(6) Adherent surface contamination property Adhesive film test piece of 50 × 100 mm area is attached to a stainless steel plate, left to stand at 60 ° C. × 90% RH for one week, and then the test piece is peeled off. The presence or absence of contamination such as cloudiness on the surface and adhesive residue was determined with the naked eye according to the following criteria.

○: No fogging or adhesive residue on the stainless steel plate surface △: Slightly fogging or adhesive residue on the stainless steel plate surface ×: Significant fogging or adhesive residue on the stainless steel plate surface

(7) Holding power (cohesive force)
Attach the adhesive coated surface of the electronic member fixing film test piece to the stainless steel plate so that the area is 25 x 25 mm, press it once with a 2 kg load roller, and press it under the condition of 23 ° C x 65% RH. After standing for a period of time, according to JIS-Z-0237, the mixture was allowed to stand for 30 minutes in an atmosphere of 40 ° C. and 65% RH, a load of 1 kg was applied, and the displacement distance (unit: mm) after 24 hours was measured.

  From the results shown in Table 1, the electronic member fixing film of the present invention is superior in antistatic property, transparency, peelability, adherend non-contaminating property and holding power as compared with the comparative example, and moreover the adhesive strength over time. It turns out that it is excellent also in stability.

  The antistatic film for fixing an electronic member of the present invention is used, for example, for fixing to a substrate when a semiconductor wafer is polished and thinned (back grinding), and is peeled and removed after the process is completed. The The process requiring provisional fixing is the same for other electronic members (BGA substrate, CSP substrate, etc.), and the electronic member fixing film of the present invention has antistatic properties, transparency, adherend non-contaminating properties, etc. Since it is excellent, it has no adverse effect on electronic components, and can be suitably used in the production of a wide range of electronic components, which is extremely useful.

Claims (8)

Hydrocarbyl (meth) acrylate copolymer having at least one quaternary onium / organic acid group represented by the following general formula (1) in the molecular side chain on at least a part of at least one surface of the film substrate ( An antistatic film for fixing an electronic member having an adhesive layer made of A).
[In the formula, Q is N or P, and R ^{1 to} R ³ are each an organic group containing a linear, branched or alicyclic group having 1 to 20 carbon atoms which may contain O and / or N (provided that R any two of the ¹ to R ³ may be bonded to form a heterocyclic ring via O or N if necessary.), R ⁴ represents an alkyl group having 1 to 8 carbon atoms, an aromatic ring or alicyclic-containing hydrocarbon group, X ^- represents a residue of a carboxylic acid group, a sulfamic acid group and (sub) polymerizable organic acid selected from the group consisting of phosphoric acid group. ] (A) reacts a quaternary onium-carbonate ester (A2) represented by the following general formula (2) with a hydrocarbyl (meth) acrylate copolymer (A1) having an organic acid group in the molecular side chain. The film according to claim 1, which is a hydrocarbyl (meth) acrylate copolymer having a quaternary onium-organic acid group.
[In the formula, Q is N or P, and R ^{1 to} R ³ are each an organic group containing a linear, branched or alicyclic group having 1 to 20 carbon atoms which may contain O and / or N (provided that R Any two of ^{1 to} R ³ may be bonded to each other through O or N if necessary to form a heterocyclic ring.), R ⁴ and R ⁵ are each an alkyl group having 1 to 8 carbon atoms, Represents an aromatic ring or alicyclic hydrocarbon group. ] (A1) is a hydrocarbyl (meth) acrylate (a1) having 4 to 25 carbon atoms in the hydrocarbyl group, a monomer (a2) containing an organic acid group, and, if necessary, other polymerizable monomers (a3). The film according to claim 2, wherein the weight ratio of (a1) :( a2) :( a3) is (30-99.8) :( 0.2-30) :( 0-40). The film according to claim 2 or 3, wherein (A2) is a quaternary onium / carbonate ester salt obtained by reacting a tertiary amine and a carbonic acid diester. The film according to any one of claims 1 to 4, wherein the content of the quaternary onium-organic acid base represented by the general formula (1) in (A) is 0.1 to 30% by weight. Furthermore, the pressure-sensitive adhesive layer contains a crosslinking agent (B) having 2 to 5 functional groups per molecule selected from the group consisting of isocyanate, epoxy, hydrazide, aziridinyl and oxazolinyl groups. The film in any one of 1-5. Furthermore, the active energy ray polymeric compound (C) which has a 2 or more unsaturated hydrocarbon group in 1 molecule, and the polymerization initiator (D) are made to contain in an adhesive layer. The film described. Furthermore, the pressure-sensitive adhesive layer contains at least one additive (E) selected from the group consisting of a tackifier resin, a plasticizer, a filler, a pigment, an ultraviolet absorber and an antioxidant. 8. The film according to any one of 7.