JP2000086756A - Production of cationically polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cationically polymerizable resin composition, capable of omitting a process for removing a solvent after the production of the resin composition. SOLUTION: This method for producing a cationically polymerizable resin composition substantially containing no solvent comprises radically copolymerizing (a) a cationically polymerizable unsaturated monomer containing a polymerizable unsaturated group and an epoxy group or oxetane group, if necessary, with (b) one or more other polymerizable unsaturated monomers in the presence of (c) a cationically polymerizable compound having a viscosity of <=500 mPa.s at 40 deg.C, not containing a polymerizable unsaturated group and containing an epoxy group or oxetane ring. A cationically polymerizable composition comprises 100 pts.wt. of a cationically polymerizable binder component containing the cationically polymerizable resin composition obtained by the production method and 0.01-20 pts.wt. of a cation polymerization initiator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a cationically polymerizable resin composition which can omit a step of removing a solvent after production, and to a cationically polymerizable composition using this resin composition.

[0002]

2. Description of the Related Art
Photocationic polymerizable compositions that undergo cationic polymerization by light irradiation often include a polymer resin having a cationically polymerizable group as a part of the cationically polymerizable component in view of the physical properties of the resulting cured product. Have been done.

When a polymer resin having a cationically polymerizable group is blended as described above, usually, a polymer resin solution having a cationically polymerizable group synthesized in a solvent and a low-molecular-weight epoxy compound such as an epoxy compound are mixed. It is manufactured by mixing a cationically polymerizable compound having a viscosity and, if necessary, a cationic photopolymerization initiator, followed by desolvation. If the solvent removal is not performed, the solvent remains in the cured product after light irradiation, causing problems such as a decrease in the hardness of the cured product. Requires a lot of time and labor, so that labor saving in the solvent removing step has been required.

An object of the present invention is to provide a method for producing a cationically polymerizable resin composition capable of saving labor in the solvent removal step, and a cured product from the cationically polymerizable resin composition obtained by the production method. An object of the present invention is to provide a production method capable of producing a cationically polymerizable resin composition without deteriorating the physical properties of the composition.

Another object of the present invention is to provide a cationically polymerizable composition using the cationically polymerizable resin composition obtained by the above-mentioned production method.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that radical polymerization of a monomer component such as a polymerizable unsaturated monomer having a cationically polymerizable group can be carried out at a low viscosity with a polymerizable unsaturated group. The present invention has been completed by finding that the above monomer component can be polymerized without any inconvenience in the absence of a solvent by performing in the presence of a cationically polymerizable compound containing an epoxy group or an oxetane ring, without containing a solvent. Reached.

That is, the present invention relates to (a) a polymerizable unsaturated monomer containing a polymerizable unsaturated group and an epoxy group or an oxetane ring and having cation polymerizability, and if necessary, (b) other polymerizable unsaturated monomers. (C) 4
A viscosity at 0 ° C. of not more than 500 mPa · s, capable of dissolving the monomers (a) and (b), containing no polymerizable unsaturated group, and containing an epoxy group or an oxetane ring; Being substantially free of solvent and characterized by radical polymerization in the presence of the compound;
An object of the present invention is to provide a method for producing a cationically polymerizable resin composition having a viscosity at 00 ° C. of 4 Pa · s or less.

The present invention also relates to a cationic polymerization initiator (B) based on 100 parts by weight of the solid content of the cationically polymerizable binder component (A) containing the cationically polymerizable resin composition obtained by the above production method. Is contained in an amount of from 0.01 to 20 parts by weight.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The cationically polymerizable resin composition obtained by the production method of the present invention is a resin composition which can be cured by causing cationic polymerization by irradiation with light such as ultraviolet rays or heating. Hereinafter, the manufacturing method of the present invention will be described.

The components (a), (b) and (c) used in the method for producing the cationically polymerizable resin composition of the present invention are as follows.

[0011] Polymerizable unsaturated groups and epoxy groups or oxeta
Unsaturation having cationic polymerizability containing an unsaturated ring
As the monomer (a), a cationically polymerizable polymerizable unsaturated monomer (a) containing a polymerizable unsaturated group and an epoxy group or an oxetane ring (hereinafter may be abbreviated as “monomer (a)”) For example, a monomer (a-1) having a polymerizable unsaturated group and an epoxy group (hereinafter may be abbreviated as “epoxy monomer (a-1)”), and a polymerizable unsaturated group and an oxetane ring Having a monomer (a-2)
(Hereinafter may be abbreviated as “oxetane monomer (a-2)”).

Specific examples of the epoxy monomer (a-1) include polymerizable unsaturated monomers containing a (methyl) glycidyl group such as glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether; -Alicyclic epoxy group-containing polymerizable unsaturated monomers such as epoxycyclohexylmethyl (meth) acrylate. In the present invention, “(meth) acrylate” means acrylate or methacrylate.

As the oxetane monomer (a-2), for example, the following general formula (1)

[0014]

Embedded image

(In the above formula (1), R ¹ is an alkyl group having 1 to 6 carbon atoms and R ² is a hydrogen atom or a methyl group); a hydroxyl-containing oxetane (for example, 3 -Ethyl-3-hydroxymethyloxetane), a functional group that reacts with the hydroxyl group and does not substantially react with the oxetane ring (for example, isocyanate group,
(E.g., a methyl ester group) and an unsaturated monomer containing an ethylenically unsaturated group (an acryloyl group, a methacryloyl group, a vinyl group, etc.) (for example, 2-isocyanatoethyl (meth) acrylate, m-isopropenyl-α, α-
Dimethylbenzyl isocyanate, methyl (meth) acrylate, etc.).

The oxetane monomer (a-2) includes:
Among them, the compound represented by the above formula (1) is preferable,
Specific examples thereof include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, and 3- (methacryloyloxymethyl) 3 -Ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3-
(Methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-
Hexyl oxetane and the like can be mentioned.

As the monomer (a), these compounds can be used alone or in combination of two or more.

The other polymerizable unsaturated monomer (b) and the other polymerizable unsaturated monomer (b) (hereinafter, may be abbreviated as “monomer (b)”) are the same as the monomer (a)
Any polymerizable unsaturated monomer that can be copolymerized with and is other than the monomer (a) can be used without any particular limitation. Typical examples thereof include, for example, methyl (meth)
Alkyl (meth) acrylates such as acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2,3-dihydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth)
Acrylate and polyethylene glycol mono (meth)
Monoesters of polyhydric alcohols with acrylic acid or methacrylic acid, such as acrylates; hydroxyl-containing monomers such as compounds obtained by ring-opening polymerization of ε-caprolactone with the above-mentioned monoesters of polyhydric alcohols with acrylic acid or methacrylic acid; Carboxyl group-containing polymerizable unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, and maleic anhydride; N, N-dimethylaminoethyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Acrylates, aminoalkyl (meth) acrylates such as N, N-dimethylaminopropyl (meth) acrylate; acrylamide, methacrylamide, N, N
-Dimethylaminoethyl (meth) acrylamide, N,
N-diethylaminoethyl (meth) acrylamide,
(Meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide, N-methylolacrylamide, N-methylolacrylamide methyl ether, N-methylolacrylamide butyl ether or derivatives thereof; styrene, acrylonitrile, methacrylonitrile, vinyl acetate, etc. Is mentioned. These compounds can be used alone or in combination of two or more. In the present invention, “(meth) acrylamide” means acrylamide or methacrylamide.

Cationically polymerizable compound (c) Cationic polymerizable compound (c) (hereinafter referred to as “compound (c)”
Has a viscosity at 40 ° C. of 50
0 mPa · s (millipascal · second) or less, and can dissolve the monomer (a) and the monomer (b);
It is a compound containing no epoxy group or oxetane ring without containing a polymerizable unsaturated group. Compound (c)
Is preferably compatible with a copolymer of a monomer (a) and a monomer (b) produced by radical polymerization (a polymer of the monomer (a) when the monomer (b) is not used). .

Examples of the cationically polymerizable compound (c) include the following epoxy compounds and oxetane compounds.

Epoxy compound: A compound having one or more epoxy groups in one molecule, having an epoxy equivalent of 70 to 5,
000, preferably 80 to 3,000 can be suitably used, and as typical examples, for example, dicyclopentadienedioxide, (3,4-epoxycyclohexyl) methyl-3,4-epoxycyclohexanecarboxylate Bis (2,3-epoxycyclopentyl) ether, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, (3,4-epoxy-6-methyl Cyclohexyl) methyl-3,4-
Epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) acetal, bis (3,4-epoxycyclohexyl) ether of ethylene glycol, 3,4-epoxycyclohexanecarboxylic acid diester of ethylene glycol, (3 , 4-Epoxycyclohexyl) methyl alcohol, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-ethyl-3- (3,4-epoxycyclohexylmethyl) oxymethyloxetane, Epode GT300 (Daicel Chemical Industries, Ltd.) Made, trade name, trifunctional alicyclic epoxy resin), following formula

[0022]

Embedded image

[0023]

Embedded image

Epoxy compounds containing an alicyclic epoxy group such as the compounds represented by the following formulas: for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4 -Butanediol diglycidyl ether,
Neopentyl glycol diglycidyl ether, 1,6
Hexanediol diglycidyl ether, glycerin diglycidyl ether, diglycerin tetraglycidyl ether, trimethylolpropane triglycidyl ether, spiroglycol diglycidyl ether, 2,6
-Diglycidyl phenyl ether, sorbitol polyglycidyl ether, triglycidyl isocyanurate,
Epoxy compounds containing an aliphatic epoxy group such as bisphenol A diglycidyl ether, butadiene dioxide, diglycidyl phthalate and 3-ethyl-3-glycidyloxymethyloxetane; for example, vinylcyclohexenedioxide, limonenedioxide and the like; An epoxy compound containing an alicyclic epoxy group and an aliphatic epoxy group; a compound having two or more epoxy groups in one molecule among the above epoxy compounds has 6 carbon atoms.
Fatty acid-modified epoxy compounds having an epoxy group and a fatty acid ester group in one molecule obtained by reacting a fatty acid (for example, lauric acid, oleic acid, linseed oil fatty acid, etc.) with a part of an epoxy group. be able to.

Oxetane compound:

[0026]

Embedded image

A compound containing at least one oxetane ring represented by the following formula in the molecule, for example, a compound represented by the following general formula (2) or (3).

[0028]

Embedded image

(In the above formula, R ¹ has the same meaning as described above, and R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms,
Alkylene group, hydroxyalkyl group, having 2 to 2 carbon atoms
An alkoxyalkyl group optionally substituted with 10 hydroxyl groups, an aryl group optionally substituted with a hydroxyl group having 7 to 12 carbon atoms, an aralkyl group, an aryloxyalkyl group),

[0030]

Embedded image

(In the above formula, two R ^{1 s} are the same or different and have the same meaning as described above, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group, a phenylene group, a xylylene group, Represents a polyalkyleneoxy group having 4 to 30 atoms).

Representative examples of the oxetane compound represented by the general formula (2) include 3-ethyl-3-methoxymethyloxetane, 3-ethyl-3-ethoxymethyloxetane, and 3-ethyl-3-butoxymethyloxetane. , 3
-Ethyl-3-hexyloxymethyloxetane, 3-
Methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-
Allyloxymethyl oxetane, 3-ethyl-3- (2
'-Hydroxyethyl) oxymethyloxetane, 3-
Ethyl-3- (2'-hydroxy-3'-phenoxypropyl) oxymethyloxetane, 3-ethyl-3-
(2′-hydroxy-3′-butoxypropyl) oxymethyloxetane, 3-ethyl-3- [2 ′-(2 ″)
-Ethoxyethyl) oxymethyl] oxetane, 3-ethyl-3- (2'-butoxyethyl) oxymethyloxetane, 3-ethyl-3-benzyloxymethyloxetane, 3-ethyl-3- (p-tert-butylbenzyl) (Oxymethyl) oxetane and the like.

As a typical example of the oxetane compound represented by the above formula (3), in the above formula (3), both R ¹ are each an ethyl group, and R ⁴ is methylene, ethylene, propylene, butylene. And cyclohexylene, phenylene, xylylene, poly (ethyleneoxy), and poly (propyleneoxy) groups.

Examples of the oxetane compound include, in addition to the compound represented by the general formula (2) or (3), bis (3-ethyloxetanyl-3-methyl) oxide and the like.

In the production method of the present invention, the mixture of the monomer (a) and, if necessary, the monomer (b) is
It is characterized by radical polymerization in the presence of the above compound (c), and it contains substantially no solvent and has a viscosity at 100 ° C. of 4 Pa · s
(Pascal-second) or less, preferably a cationically polymerizable resin composition having a viscosity at 40 ° C. of 1 Pa · s or less can be obtained.

The mixing ratio of the sum of the monomer (a) and the monomer (b) and the compound (c) at the time of the radical polymerization reaction is not particularly limited, but the monomer (a) and the monomer (b) 20:80 to 80:20 by weight of the compound (c), more preferably 30:80.
It is preferable to be in the range of 70 to 60:40.

At the time of the above radical polymerization reaction, a radical polymerization initiator can be used to accelerate the reaction.
As the radical polymerization initiator, known radical polymerization initiators can be used without particular limitation. Specific examples thereof include benzoyl, ditert-butylhydroperoxide, tert-butylhydroperoxide, and cumyl peroxide. , Cumene hydroperoxide,
Diisopropylbenzene hydroperoxide, tert
-Butylperoxybenzoate, lauryl peroxide, acetyl peroxide, tert-butyl-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxide Peroxides such as oxy-2-ethylhexanoate; 2,2'-azobisisobutyronitrile, 2,2
And azo compounds such as' -azobisisobutyronitrile, azobisdimethylvaleronitrile, and azobiscyclohexanecarbonitrile. These are 1
They can be used alone or in combination of two or more.

At the time of the radical polymerization reaction, it is preferable not to use a solvent because the solvent removing step can be omitted, but a small amount of a solvent may be blended. Even when a solvent is required to be removed by a solvent removal step, since the compound (c) is blended, the amount of the compounded solvent can be reduced, and the solvent removal time can be shortened.

The conditions of the above radical polymerization reaction are not particularly limited, but are usually about 50 to 200 ° C., preferably about 70 to 150 ° C. for about 1 to 24 hours, preferably about 5 to 10 hours. Time ranges are preferred.

By the above radical polymerization reaction, a copolymer of monomer (a) and monomer (b) (monomer (b)
When is not used, a polymer of the monomer (a)) (hereinafter sometimes abbreviated as "radical polymer") is produced. At the time of the radical polymerization reaction, the compound (c)
A substance which functions similarly to a solvent, such as lowering the viscosity of a reaction system, and which does not substantially react by itself can be used.

The radical polymer obtained by the above radical polymerization reaction has a number average molecular weight of 500 to 200,000.
0, preferably from 1,000 to 100,000, more preferably from 2,000 to 20,000, from the viewpoints of curability, coating workability, etc., and also an epoxy group and / or One oxetane ring per molecule
Or more, preferably an average of 2 to 100 in total of the epoxy group and the oxetane ring, and more preferably an average of 2 to 2
It is suitable to have 50. When the radical polymer has only an epoxy group as a cationically polymerizable site, the epoxy group equivalent is in the range of 130 to 15,000, preferably 140 to 7,000, and only the oxetane ring is used. If so, the oxetane ring equivalent is from 130 to 15,000, preferably from 140 to 7000.
When the cationically polymerizable site has both an epoxy group and an oxetane ring, it is preferable that both of them be one group. It is appropriate that the equivalent weight is in the range of 130 to 15,000, preferably 140 to 7,000 from the viewpoint of curability, suppression of volume shrinkage during curing, surface appearance of the cured product, and the like.

In the production method of the present invention, when a solvent is not used during the radical polymerization reaction, the radical polymerization reaction is carried out as it is, and when a solvent is used, the solvent is removed as required to obtain a radical polymerization reaction. The target is a mixture of the union and the compound (c), which is substantially free of a solvent and has a viscosity at 100 ° C. of 4 Pa · s.
Hereinafter, a cationically polymerizable resin composition having a viscosity at 40 ° C. of preferably 1 Pa · s or less can be obtained.

Cationic Polymerizable Composition The cationic polymerizable composition of the present invention can be prepared by blending a cationic polymerization initiator (B) with a cationic polymerizable binder component (A) containing the cationic polymerizable resin composition obtained by the production method of the present invention. A polymerizable composition can be obtained.

Cation-polymerizable binder component (A) The cation-polymerizable binder component (A) may consist of only the cation-polymerizable resin composition, but may contain other cation-polymerizable compounds as required. be able to. Examples of the other cationically polymerizable compound include the above-mentioned cationically polymerizable compound (c).

The mixing ratio of the cationically polymerizable resin composition and the other cationically polymerizable compound in the cationically polymerizable binder component (A) is not particularly limited, but is usually 100: The range is from 0 to 50:50, preferably from 100: 0 to 70:30.

Cationic Polymerization Initiator (B) The cationic polymerization initiator (B) to be added to the cationically polymerizable composition of the present invention can be prepared by irradiating an epoxy group or the like in the cationically polymerizable resin composition by irradiation with light such as ultraviolet rays or heating. Promotes cationic polymerization of cationically polymerizable groups such as oxetane rings,
It is blended to make the curing proceed smoothly.
Examples of the cationic polymerization initiator include compounds that generate a substance that initiates cationic polymerization such as an acid by light such as ultraviolet light or heating.

Examples of the cationic polymerization initiator include, for example, compounds represented by the following formulas.

Ar ₂ I ⁺ · X ⁻ (wherein, Ar represents an aryl group, for example, a phenyl group;
X ^- is ^{_{BF 4 -, PF 6 -,}} SbF 5 (OH) -, Sb
F ₆ ^-, AsF ₆ ^- or the following formula

[0049]

Embedded image

[0050] a group represented _{^{by) Ar 3 S + · X -}} (4) ( wherein, Ar and X ^- is the same as defined above)

[0051]

Embedded image

(Wherein, R ⁵ represents an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms;
Represents an integer of 3 to 3, and X ^- has the same meaning as described above)

[0053]

Embedded image

(Wherein, Y ⁻ represents PF ₆ ⁻ , SbF ₆ ⁻ or AsF ₆ ⁻ or SbF ₅ (OH) ⁻ )

[0055]

Embedded image

(Wherein, X ^- has the same meaning as described above)

[0057]

Embedded image

(Wherein, X ⁻ has the same meaning as described above)

[0059]

Embedded image

(Wherein, X ^- has the same meaning as described above)

[0061]

Embedded image

[0062] (wherein, R ⁶ is an alkenyl group having an aralkyl group, or -C 3-9 of 7 to 15 carbon atoms, R ⁷ is a hydrocarbon group or a hydroxyphenyl group having 1 to 7 carbon atoms, R ⁸ Represents an alkyl group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, and X ^- has the same meaning as described above)

[0063]

Embedded image

(In the formula, R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 12 carbon atoms or a group having 1 to 12 carbon atoms.
Represents an alkoxy group)

[0065]

Embedded image

(Wherein R ⁹ and R ¹⁰ have the same meaning as described above)

[0067]

Embedded image

[0068]

Embedded image

(Wherein R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and X ⁻ has the same meaning as described above.) Have)

[0070]

Embedded image

(Wherein R ¹² and R ¹³ are each independently
A hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and X ⁻ has the same meaning as described above.) A mixture of Ar ₃ Si—OOH and an aluminum chelate (wherein , Ar has the same meaning as described above) Examples of the cationic polymerization initiator include, in addition to the above, boron trifluoride, tetraethylammonium bromide, and the like. The cationic polymerization initiator can be used singly or as a mixture of two or more, and a thermal cationic polymerization initiator and a photocationic polymerization initiator can be used in combination.

Among the above cationic polymerization initiators, the aromatic cationic sulfonium salt represented by the above formula (4), (5) or (6) is preferable as the thermal cationic polymerization initiator.
The aromatic sulfonium salt imparts excellent low-temperature curability to the composition of the present invention, and can cure a coating film from the composition of the present invention by heating at about 80 ° C. or more. Since it does not show a catalytic action, it does not deteriorate storage stability.

Specific examples of the aromatic sulfonium salt include, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, and 4-acetoxyphenylbenzylmethylsulfonium hexafluoro Antimonate, 4
-Acetoxyphenyldimethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-
3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, benzyl-3-methyl-4-hydroxy-5-tert-butylphenylmethylsulfonium hexafluoroantimonate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, dibenzyl-4-
Hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, nitrobenzyl-4
-Hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dinitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, β-naphthylmethyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate and the like.

Commercially available aromatic sulfonium salts include, for example, San-Aid SI-L85 and SI-L11
0, same SI-L145, same SI-L160, same SI-H
15, same SI-H20, same SI-H25, same SI-H4
0, same SI-H50, same SI-60L, same SI-80
L, SI-100L, SI-110L, SI-1
80L, SI-80, and SI-100 (all of which are manufactured by Sanshin Chemical Industry Co., Ltd., trade names).

Commercially available photocationic polymerization initiators include, for example, Cyracure UVI-6970 and UVC
I-6974 and UVI-6990 (both manufactured by Union Carbide Co., USA), Irgacure 26
1, 264 (all of which are Ciba Specialty
Chemicals), CIT-1682 (Nippon Soda Co., Ltd.)
), BBI-102 (manufactured by Midori Kagaku), Adeka Optomer SP-150, and SP-170 (all manufactured by Asahi Denka Co., Ltd.).

Some of the cationic polymerization initiators function as both a cationic photopolymerization initiator and a thermal cationic polymerization initiator, and have a function of initiating cationic polymerization both by light and by heating.

The amount of the cationic polymerization initiator to be added is curable,
From the viewpoint of storage stability, processability of the cured product, finished appearance, and the like, it is usually 0.01 to 20 parts by weight, preferably 0.0 to 20 parts by weight, based on 100 parts by weight of the cationically polymerizable binder component (A).
The range is preferably 5 to 15 parts by weight, more preferably 0.1 to 10 parts by weight.

The cationically polymerizable composition of the present invention may contain, if necessary, a coloring pigment and a binder component having no cationically polymerizable component, in addition to the above-mentioned cationically polymerizable binder component (A) and the cationic polymerization initiator (B). Contains a polymerization accelerator, a filler, a pigment dispersant, a fluidity regulator, a leveling agent, an antifoaming agent, a light stabilizer, an antioxidant, a thermal polymerization inhibitor, a lubricity imparting agent such as wax, etc. it can.

The above-mentioned coloring pigments which can be incorporated as required include coloring pigments usually used in the field of paints and printing, for example, white pigments such as titanium white and zinc white; blue pigments such as cyanine blue and indaslen blue; Green pigments such as cyanine green and patina; organic red pigments such as azo and quinacridone; inorganic red pigments such as red iron; organic yellow pigments such as benzimidazoline, isoindolinone, isoindoline and quinophthalone; titanium yellow; Inorganic yellow pigments such as graphite; black pigments such as carbon black, graphite, and pine smoke; brilliant pigments such as aluminum powder, copper powder, nickel powder, mica powder coated with titanium oxide, mica powder coated with iron oxide, and brilliant graphite; Is mentioned.

As the coloring pigment, a neutral or acidic coloring pigment is preferably used since it does not inhibit cationic polymerization, and a pigment having a pigment surface treated to be neutral or acidic is also preferably used. Can be.

The amount of the coloring pigment in the composition of the present invention is suitably not more than 500 parts by weight, preferably in the range of 300 parts by weight, based on 100 parts by weight of the cationically polymerizable binder component (A). .

Examples of the binder component having no cationic polymerizability, which is optionally added to the composition of the present invention, include:
For example, an acrylic resin, a polyester resin, a rosin-modified phenolic resin, a rosin-modified alkyd resin, a ketone resin, or the like can be blended for the purpose of improving the viscosity of the composition and improving the physical properties and adhesion of the obtained cured product. The compounding amount of the binder component having no cationic polymerizability is preferably within a range of 20 parts by weight or less based on 100 parts by weight of the cationically polymerizable binder component (A) in terms of curability and the like.

Examples of the polymerization accelerator that can be added to the composition of the present invention as needed include alkyl phosphines such as triphenylphosphine and thioethers such as β-thiodiglycol. These can be used alone or in combination of two or more.

The cationically polymerizable composition of the present invention obtained as described above can be suitably used as a paint, ink, adhesive, resist material and the like.

The composition of the present invention can be applied to paper, plastic, metal, glass, wood, and a substrate obtained by combining these. For example, the coating amount of the composition of the present invention on the surface of these substrates is 1 to 50 μm, preferably 2
The coating can be performed so as to be within the range of ３０30 μm, and then cured by light irradiation or heating.

The coating means can be applied by a coating or printing method such as roll coater coating, spray coating, brush coating, bar coater coating, roller coating, screen printing, flat pressure printing, rotary printing and the like.

When the composition of the present invention contains a cationic photopolymerization initiator as a cationic polymerization initiator, it can be cured by irradiation with light, and when it contains a thermal cationic polymerization initiator, it can be cured by heating. Can be cured.

When the applied composition of the present invention is cured by irradiation with light, when the composition of the present invention contains a solvent, the solvent is removed by heating or the like, and then irradiation with light such as ultraviolet rays is performed. preferable. Light irradiation conditions are
The wavelength of light to be applied can be changed as appropriate depending on the type and thickness of the coated composition.
The range of 00 to 450 nm is appropriate, and an irradiation source having a wavelength with high sensitivity can be appropriately selected and used according to the type of the cationic photopolymerization initiator.

As a light irradiation source such as ultraviolet light, for example,
Examples include a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, and sunlight. The dose at the time of light irradiation is usually 10 to 200
0 mJ / cm ² , preferably 50 to 1000 mJ / cm
^A range of ² is suitable. After the light irradiation, heating may be performed. In some cases, the curing may be further advanced by heating, or the stress distortion of the cured product may be reduced, and the hardness and adhesion of the coating film may be improved. The heating is usually 150 to
It can be carried out at an atmosphere temperature of 400 ° C. for 5 seconds to 30 minutes.

When the applied composition of the present invention is cured not by light irradiation but by heating, it is usually from 80 to 200.
It is preferable to heat at an ambient temperature of 30 ° C. for 30 seconds to 5 hours.

In the present invention, the effects of the present invention are particularly remarkably exerted on a cationically polymerizable composition which is hardened by irradiation with light such as ultraviolet rays, in which mixing of a solvent is avoided at the time of curing.

[0092]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Hereinafter, both “parts” and “%” are based on weight.

Production of Cationic Polymerizable Resin Compositions Examples 1 and 2 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane was placed in a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device. The carboxylate was charged in the amount shown in Table 1 below, and heated to 110 ° C. while blowing nitrogen gas. Then, a monomer and a polymerization initiator 2, 2 shown in Table 1 below were added thereto from a dropping device.
A mixed solution with 2′-azobis (2-methylbutyronitrile) was added dropwise over about 3 hours. After dropping, 110 ° C
And the reaction is terminated by aging for 2 hours with 3,4-epoxycyclohexylmethyl-cationic polymerizable acrylic resin.
A transparent cationically polymerizable resin composition which was a mixture with 3,4-epoxycyclohexanecarboxylate was obtained.
3,4-epoxycyclohexylmethyl-3 used
4-epoxycyclohexanecarboxylate is 40
The viscosity at ° C was about 200 mPa · s (based on a B-type viscometer at a rotation speed of 6 rpm).

Examples 3 and 4 1,6-hexanediol diglycidyl ether was charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device in an amount shown in Table 1 below, and nitrogen gas was used. The temperature was raised to 110 ° C. while blowing. Then, a mixed solution of a monomer shown in Table 1 below and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into the dropping device over about 3 hours. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 2 hours to terminate the reaction, thereby obtaining a transparent cationically polymerizable resin composition which was a mixture of a cationically polymerizable acrylic resin and 1,6-hexanediol diglycidyl ether. The 1,6-hexanediol diglycidyl ether used had a viscosity of about 1 at 40 ° C.
The viscosity was 5 mPa · s (based on a B-type viscometer at a rotation speed of 6 rpm).

Examples 5 and 6 3-Ethyl-3-hydroxymethyloxetane was charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device in an amount shown in Table 1 below, and nitrogen gas was added. The temperature was raised to 110 ° C. while blowing. Then, a monomer shown in Table 1 below and 2,2′-azobis (2-methylbutyronitrile), which is a polymerization initiator, were added thereto from a dropping device.
Was added dropwise over about 3 hours. After dropping,
The reaction was completed by aging at 110 ° C. for 2 hours to obtain a transparent cationically polymerizable resin composition which was a mixture of a cationically polymerizable acrylic resin and 3-ethyl-3-hydroxymethyloxetane. The used 3-ethyl-3-hydroxymethyloxetane has a viscosity at 40 ° C. of about 5 mPa · s.
(Measured by a B-type viscometer at a rotation speed of 6 rpm).

Comparative Example 1 100 parts of toluene was charged into a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device, and heated to 110 ° C. while blowing nitrogen gas. Then, a mixed solution of a monomer shown in Table 1 below and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into the dropping device over about 3 hours. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 2 hours, and then cooled to room temperature to terminate the reaction, thereby obtaining a cationically polymerizable acrylic resin solution having a nonvolatile content of about 50%. Next, 100 parts of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was mixed with 200 parts of the cation-polymerizable acrylic resin solution, and the mixture was heated to 110 ° C. Was removed under reduced pressure for 3 hours to obtain a transparent cationically polymerizable resin composition which was a mixture of a cationically polymerizable acrylic resin and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. .

Comparative Example 2 A reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device was charged with 45 parts of toluene, and the temperature was raised to 110 ° C. while blowing nitrogen gas. Then, a mixed solution of a monomer shown in Table 1 below and 2,2′-azobis (2-methylbutyronitrile) as a polymerization initiator was dropped into the dropping device over about 3 hours. After completion of the dropwise addition, the mixture was aged at 110 ° C. for 2 hours, and then cooled to room temperature to terminate the reaction to obtain a cationically polymerizable acrylic resin solution having a nonvolatile content of about 69%. Subsequently, 45 parts of 3-ethyl-3-hydroxymethyloxetane was mixed with 145 parts of the cationically polymerizable acrylic resin solution, and the mixture was heated to 110 ° C.
Using a vacuum pump, the pressure inside the reaction vessel was reduced to remove toluene over 3 hours to obtain a transparent cationically polymerizable resin composition which was a mixture of a cationically polymerizable acrylic resin and 3-ethyl-3-hydroxymethyloxetane. Was.

The viscosities at 100 ° C. of the cationically polymerizable resin compositions obtained in Examples 1 to 6 and Comparative Examples 1 and 2 (measured with a B-type viscometer at a rotation speed of 6 rpm) Table 1 below shows the number average molecular weight of the cationically polymerizable acrylic resin in the composition as measured by gel permeation chromatography (GPC), and the epoxy equivalent and oxetane ring equivalent of the acrylic resin.

[0099]

[Table 1]

(Note) in Table 1 has the following meanings.

(* 1) Alicyclic compound-1: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate. (* 2) Aliphatic compound-2: 1,6-hexanediol diglycidyl ether.

(* 3) Oxetane compound-3: 3-ethyl 3-hydroxymethyloxetane.

Example 7 The cationically polymerizable resin composition (d) 1 obtained in Example 1 above
In 00 parts, the cationic polymerization initiator “Siracure U” was added.
VI-6990 "(manufactured by Union Carbide, USA)
5 parts (trade name, abbreviated as "UVI-6990" in Table 2) were added, and the mixture was charged into a stirring and defoaming machine and kneaded for 3 minutes to obtain a cationically polymerizable composition. This composition has a thickness of 10
After coating the surface of a 0 μm polyethylene terephthalate film with a roll coater to a thickness of 5 μm, the dose is 150 mJ using a metal halide lamp.
/ Cm ² to obtain a cured coating film.

Example 8 The procedure of Example 7 was repeated except that the cationically polymerizable resin composition (d) 1
Instead of 00 parts, 100 parts of the cationically polymerizable resin composition (i) obtained in Example 6 was used, and as a cationic polymerization initiator, instead of 5 parts of “Siracure UVI-6990”, 2 parts of “ A cured film was obtained in the same manner as in Example 7, except that "BBI-102" (trade name, manufactured by Midori Kagaku Co., Ltd., diallyliodonium salt-based photocationic polymerization initiator) was used.

Example 9 The cationically polymerizable resin composition (e) 1 obtained in Example 2 above
To 00 parts, 6 parts of “Siracure UVI-6990” were added, and the mixture was stirred at 1,000 rpm for 1 minute with a stirrer.
The mixture was stirred for 0 minutes to obtain a cationically polymerizable composition. The composition was coated on a surface of an aluminum plate having a thickness of 500 μm with a bar coater so as to have a thickness of 8 μm, and then cured by irradiating ultraviolet rays using a metal halide lamp so that the dose became 400 mJ / cm ^2. A coating was obtained.

Example 10 The procedure of Example 9 was repeated except that the cationically polymerizable resin composition (e) 1
Instead of 00 parts, 100 parts of the cationically polymerizable resin composition (f) obtained in Example 3 was used, and as a cationic polymerization initiator, instead of 6 parts of “Siracure UVI-6990”, 3 parts of “ A cured coating film was obtained in the same manner as in Example 9 except that "BBI-102" was used.

Example 11 The cationically polymerizable resin composition (g) 1 obtained in Example 4 above
In 00 parts, a cationic polymerization initiator "San-Aid SI
-180L "(manufactured by Sanshin Chemical Industry Co., Ltd., thermal cationic polymerization initiator, trade name, abbreviated as" SI-180L "in Table 2), charged into a stirring defoaming machine, and kneaded for 3 minutes. As a result, a cationically polymerizable composition was obtained. The composition was coated on a surface of an aluminum plate having a thickness of 500 μm by a bar coater so as to have a thickness of 8 μm.
After heating for a minute, a cured coating film was obtained.

Example 12 The cationically polymerizable resin composition (h) 1 obtained in Example 5 above
To 100 parts, 100 parts of titanium white was added, and the mixture was charged into a stirring and defoaming machine, kneaded for 10 minutes, and then dispersed with a three-roll mill to obtain a white cationically polymerizable composition. This composition was coated on a surface of a polyethylene terephthalate film having a thickness of 100 μm by a roll coater so as to have a thickness of 6 μm, and then irradiated with ultraviolet rays using a metal halide lamp so that the dose became 150 mJ / cm ^2. Thus, a cured coating film was obtained.

Example 13 The cationically polymerizable resin composition (g) 1 obtained in Example 4 above
To 5 parts, 85 parts of ethylene glycol diglycidyl ether, which is a cationic polymerizable compound, and 3 parts of “Siracure UVI-6990” as a cationic polymerization initiator were added,
The mixture was stirred for 10 minutes with a stirrer under the condition of the number of rotations of 1000 rpm to obtain a cationically polymerizable composition. The composition was coated on a surface of an aluminum plate having a thickness of 500 μm with a bar coater so as to have a thickness of 8 μm, and then cured by irradiating ultraviolet rays using a metal halide lamp so that the dose became 400 mJ / cm ^2. A coating was obtained.

Example 14 The cationically polymerizable resin composition (g) 2 obtained in Example 4 above
In 5 parts, a cationically polymerizable compound, 3-ethyl-3-
75 parts of hexyloxymethyl oxetane and 5 parts of "Sun Aid SI-180L" as a cationic polymerization initiator were added, and the mixture was charged into a stirring defoaming machine and kneaded for 3 minutes to obtain a cationically polymerizable composition. This composition was coated on a surface of an aluminum plate having a thickness of 500 μm by a bar coater so as to have a thickness of 8 μm, and then heated at 180 ° C. for 30 minutes to obtain a cured coating film.

Comparative Example 3 The cationically polymerizable resin composition (j) 1 obtained in Comparative Example 1 above
In 00 parts, “Cyracure U” was used as a cationic polymerization initiator.
VI-6990 "was added thereto, and the mixture was charged into a stirring and defoaming machine.
The mixture was kneaded for 3 minutes to obtain a cationically polymerizable composition. This composition was coated on a surface of a polyethylene terephthalate film having a thickness of 100 μm by a roll coater so as to have a thickness of 5 μm, and then irradiated with ultraviolet rays using a metal halide lamp so that the dose became 150 mJ / cm ^2. Thus, a cured coating film was obtained.

Comparative Example 4 In Comparative Example 3, 100 parts of the cationically polymerizable resin composition (k) obtained in Comparative Example 2 was used instead of the cationically polymerizable resin composition (j), and a cationic polymerization initiator was used. A cured coating film was obtained in the same manner as in Comparative Example 3, except that 2.5 parts of "BBI-102" was used instead of 5 parts of "Siracure UVI-6990".

The cured coating films obtained in Examples 7 to 14 and Comparative Examples 3 and 4 were tested for their appearance, pencil hardness and surface curability according to the following test methods. The test results are shown in Table 2 below.

Test Method Coating Appearance: The smoothness, cracking, and glossiness of the coating film were visually observed and evaluated according to the following criteria.

：: There is no abnormality in the coating film, and good. Δ: Slightly poor smoothness or gloss, but no crack is observed. ×: Crack is observed, or the smoothness or gloss is extremely poor.

Pencil hardness: JIS K-5400
A pencil scratch test specified in 4.2 (1990) was performed, and an evaluation based on scratches was performed.

Surface curability: The surface of the cured coating film was rubbed back and forth with a gauze impregnated with methyl ethyl ketone under a pressure of about 1 kg / cm ² , and the glossiness of the coating film surface was evaluated according to the following criteria.

◎: Little change in glossiness of the coated surface was observed even after 5 reciprocations. ○: Significant change in gloss was observed on the coated surface after 5 reciprocations, but almost no change in gloss after 2 reciprocations. Not observed, x: A considerable change in glossiness of the coated surface is observed after reciprocation.

[0119]

[Table 2]

Comparative Example 1 is different from Example 1 in that the polymerization of the monomer was carried out in an organic solvent instead of in the cationically polymerizable compound (c), and the resulting cationically polymerizable acrylic resin solution was mixed with the cationically polymerizable compound (c). Is mixed and then the solvent is removed to obtain a cationically polymerizable resin composition. The production time of the cationically polymerizable resin composition was about 5 hours in Example 1 and about 9 hours in Comparative Example 1 due to the desolvent step. As is clear from Table 1, the cationically polymerizable acrylic resin in Example 1 has properties comparable to those of the cationically polymerizable acrylic resin of Comparative Example 1. Example 7 using the cationically polymerizable resin composition of Example 1
Corresponds to Comparative Example 3 using the cationically polymerizable resin composition of Comparative Example 1, and Example 7 and Comparative Example 3 show the same coating film performance as is clear from Table 2. I have.

In Comparative Example 2, the polymerization of the monomer in Example 6 was carried out in an organic solvent instead of in the cationically polymerizable compound (c), and the resulting cationically polymerizable acrylic resin solution was mixed with the cationically polymerizable compound (c). Is mixed and then the solvent is removed to obtain a cationically polymerizable resin composition. The production time of the cationically polymerizable resin composition was about 5 hours in Example 6 and about 9 hours in Comparative Example 2. As is clear from Table 1, the cationically polymerizable acrylic resin in Example 6 has properties comparable to those of the cationically polymerizable acrylic resin of Comparative Example 2. Example 8 using the cationically polymerizable resin composition of Example 6 corresponds to Comparative Example 4 using the cationically polymerizable resin composition of Comparative Example 2,
As is clear from Table 2, Example 8 and Comparative Example 4 show the same coating film performance.

[0122]

According to the method for producing a cationically polymerizable resin composition of the present invention, the solvent removal step can be omitted or labor can be saved, and the production step can be shortened. The cured product obtained by curing the cationically polymerizable resin composition obtained by the production method of the present invention can have good physical properties, and the production method of the present invention does not reduce the physical properties of the cured product. Things.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Michichi Kato 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Kansai Paint Co., Ltd. (72) Inventor Ken Matsuda 4-1-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F term (reference) in Kansai Paint Co., Ltd.

Claims (6)

[Claims] 1. A polymerizable unsaturated monomer having (a) a cationically polymerizable monomer containing a polymerizable unsaturated group and an epoxy group or an oxetane ring and, if necessary, (b) another polymerizable unsaturated monomer. (C) a viscosity at 40 ° C. of 500 mPa · s or less, capable of dissolving the monomers (a) and (b), containing no polymerizable unsaturated group, and containing an epoxy group or an oxetane ring. A method for producing a cationically polymerizable resin composition substantially free of a solvent and having a viscosity at 100 ° C. of 4 Pa · s or less, characterized in that radical polymerization is carried out in the presence of a cationically polymerizable compound. 2. The method according to claim 1, wherein the radical polymerization reaction is carried out substantially in the absence of a solvent. 3. The method according to claim 1, wherein the number average molecular weight of the polymer obtained by radical polymerization is in the range of 500 to 200,000. 4. The compounding ratio of the total of the polymerizable unsaturated monomer (a) having cationic polymerizability and the other polymerizable unsaturated monomer (b) and the cationic polymerizable compound (c) is as follows:
20:80 by weight ratio of the sum of (a) and (b) :( c)
2. The method according to claim 1, wherein the value is in the range of 80 to 20.
The method according to any one of claims 1 to 3. 5. A cation polymerizable binder component (A) containing the cation polymerizable resin composition obtained by the production method according to claim 1 based on 100 parts by weight of a solid content.
(B) A cationically polymerizable composition comprising 0.01 to 20 parts by weight of a cationic polymerization initiator. 6. The coloring pigment is further added to the cationic polymerizable binder component (A) in an amount of 1 to 100 parts by weight based on 100 parts by weight of the solid content.
The cationically polymerizable composition according to claim 5, which is contained in an amount of 500 parts by weight.