JPH03122107A - Active energy ray-setting composition - Google Patents

Abstract

PURPOSE:To obtain the subject new composition useful for a pressuresensitive adhesive without fear of harmfulness or fire, etc., exhibiting tackiness after curing and excellent in coating properties at room temperature, containing specific components, not containing an organic solvent nor an acrylic monomer having low boiling point. CONSTITUTION:The aimed composition contains (A) a comb-type polyester having OH group and (meth)acryloyloxy group at chain end and having alkyl side chain directly bonding to main chain through ester bonding or ether bonding, (B) a monofunctional acrylate expressed by formula I (R<1> is 4-18C alkyl) and/or (C) a monofunctional acrylate expressed by formula II [X is expressed by formula III or formula IV (m is 2-7; l is 1-7; R<2> is H or methyl; Y is dibasic acid residue)]. Besides, e.g., 2-hydroxy-3-butyloxypropyl acrylate is exemplified as the component B and e.g., succinic acid monoacryloyloxy ethyl ester is exemplified as the component C.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The composition of the present invention can be used by irradiation with active energy rays such as electron beams (hereinafter referred to as EB) or ultraviolet rays (hereinafter referred to as U). It has the property of curing and is particularly suitable for forming a pressure-sensitive adhesive with excellent physical properties, and is useful as a pollution-free pressure-sensitive adhesive composition that essentially does not require the use of a solvent.

[Prior Art] In recent years, adhesives containing organic solvents have problems such as toxicity to workers, fire danger, environmental pollution, drying speed, and wastage of resources (solvents). Solvent-free adhesives that do not contain as an essential component and utilize curing by irradiation with active energy rays are being considered.

As a solvent-free adhesive, one in which an acrylic polymer is dissolved in an acrylic monomer having a low boiling point such as butyl acrylate or 2-ethylhexyl acrylate is known. Since the acrylic monomer in this adhesive has a low boiling point, it has a problem of having a unique odor, and furthermore, it has not always been able to satisfy the physical properties required for an adhesive, such as adhesive strength.

Recently, 1°000 to 10
An acrylate having a special polyester structure (hereinafter referred to as special polyester acrylate) having a molecular weight of 1,000 was developed (Japanese Patent Laid-Open No. 11723/1986). This product is characterized by having an alkyl side chain bonded to the main chain via an ester bond or an ether bond involving a third or more polyester-forming functional group of the polyester-forming compound constituting the main chain. Compared to conventional acrylic polymers containing butyl acrylate, 2-ethylhexyl acrylate, etc., it has a lower molecular weight and its cured product exhibits excellent adhesive properties.

However, although the above-mentioned special polyester acrylate has the property of lowering the viscosity with slight heating compared to normal polyester, even when heated to 50°C, the viscosity is 50,000 to 400,000 cps. Due to its high viscosity, there is a problem in that it cannot be coated uniformly at room temperature. Therefore, when actually performing coating using special polyester acrylate, in order to satisfy fluidity, coating properties, leveling properties, etc., it is necessary to use hot-melt coating that allows the special polyester acrylate to be heated to 80°C or higher. Expensive specialized coating equipment such as a coater is required.

Furthermore, even when coating with such expensive equipment, it is easily affected by the difference in outside temperature between summer and winter, so obtaining a stable and uniform coating requires only highly skilled technicians. This is a difficult task for many people.

Also, special polyester acrylate is not heated sufficiently,
If the coating is applied while the viscosity is still high, a so-called misting phenomenon occurs in which the resin scatters in the form of mist at the rotating part of the roll coater, which not only contaminates the working environment but also makes it impossible to obtain a good coating. be.

One possible way to solve these problems is to dilute the special polyester acrylate with a low-viscosity vinyl compound that can reduce the viscosity. When the acrylate is diluted, the originally excellent adhesive properties of the special polyester acrylate are significantly reduced in the cured product, making it impossible to obtain a product with practical use.

[Problems to be Solved by the Invention] The present invention essentially does not contain an organic solvent or a low-boiling acrylic monomer, and after curing by irradiation with active energy rays such as UV or EB, It is an object of the present invention to provide a novel composition that can exhibit adhesive properties and has excellent coatability at room temperature.

Therefore, the present invention solves various problems in the prior art, such as toxicity to workers, fire danger, environmental pollution, odor control, drying speed, waste of resources (solvent), workability, etc. This significantly improves physical properties.

(B) Structure of the invention [Means for solving the problem] As a result of intensive study, the present inventors have found that in addition to the component CA shown below, the component [B] and/or component [C] and a diluent. It was discovered that a polymer having excellent properties as a pressure-sensitive adhesive can be obtained by containing the above-mentioned components, and the present invention was completed based on this discovery.

That is, the present invention is an active energy ray-curable composition characterized by containing the following component [A] and [B] component and/or the following component [C].

[A]: A comb-shaped polyester having a hydroxyl group and a (meth)acryloyloxy group at the molecular terminal, and an alkyl side chain directly bonded to the main chain via an ester bond or an ether bond.

[B]: CM,=CHC0CHICHCH,OR
'1 0 0H (In the above formula, R' represents an alkyl group having 4 to 18 carbon atoms.) [C]: CH2=cHcOXH 1 (In the above formula, X represents the following (1) or (2) (2) -CHtCHOCY - CO- 111 R"OO (In the above formula, Rg is hydrogen or a methyl group, and Y is a dibasic acid residue.) Each component in the composition of the present invention will be explained in detail below. In this specification, (Meth)acrylic acid represents acrylic acid and/or methacrylic acid, and (meth)acrylate represents acrylate and/or methacrylate.

The [A] component and the [A] component in the present invention have a hydroxyl group and (
A comb containing a meth)acryloyloxy group and having an alkyl side chain bonded to the main chain via an ester bond or an ether bond involving a third or more polyester-forming functional group of a polyester-forming compound constituting the main chain. It is a type-structured polyester and is a basic component when the composition of the present invention is used as an adhesive composition.

It is obtained by reacting component [A], for example, a basic polyester having a hydroxyl group and an alkyl side chain, with a (meth)acrylate compound.

First, the basic polyester will be explained.

The main chain of the basic polyester is a combination of a large number of ester constituent units consisting of divalent or higher polycarboxylic acids and divalent or higher polyols, and the ester-forming functionality of the third or higher carboxyl group or hydroxyl group in this ester constituent unit The alkyl side chains are attached to the main chain through ester or ether linkages involving groups.

The alkyl side chains are preferably formed in 90% or less of all ester structural units, and the number of alkyl side chains per ester structural unit is 0 on average.
．． The number is preferably 0.02 to 2, more preferably 0.05 to 1.

The main chain of the basic polyester has no branched carbon chains other than the alkyl side chains mentioned above, and is essentially straight, with the exception of a few side chains originating from the polycarboxylic acid or polyol that constitute the main chain. It has a chain structure. Therefore, the basic polyester has a comb-shaped structure in which alkyl side chains are uniformly bonded to the main chain.

The molecular weight of the basic polyester has a wide distribution,
The weight average molecular weight is preferably 1.000 to 10.000, more preferably 2,000 to 5,000.

The hydroxyl value of the basic polyester is 10 to 10100KO
Preferably it is H/g. This hydroxyl group is important for reacting a compound having reactivity or crosslinking properties with respect to the basic polyester, such as a (meth)acrylate compound described below.

The glass transition temperature of the basic polyester is less than 0°C -60
The amorphous product is preferably an amorphous product with a temperature of at least 120°C and more preferably at least 20°C and 60°C or more.

In the main chain of the basic polyester, only two carboxyl groups of the polycarboxylic acid and only two hydroxyl groups of the polyol or on average only two polyester-forming hydroxyl and carboxyl groups of the hydroxycarboxylic acid are bonded. It is necessary and starting @ to constitute the basic polyester backbone! In addition to the customary dicarboxylic acids such as aliphatic dicarboxylic acids or aromatic dicarboxylic acids, diols and hydroxycarboxylic acids, in particular alkyl esters of at least trifunctional carboxylic acids, in particular monoesters of tricarboxylic acids and tetracarboxylic acids. Diesters of acids, alkyl esters of at least trifunctional polyols, in particular aliphatic monoesters of triols and diesters of tetraols and alkyl esters of at least trifunctional hydroxycarboxylic acids, in particular monohydroxydicarboxylic acids or dihydroxymonocarboxylic acids. Preference is given to using monoalkyl esters.

Also, instead of the monoalkyl ester of at least trifunctional or higher aliphatic or aromatic polycarboxylic acid or the monoalkyl ester of at least trifunctional polyol,
In many cases it is also possible to use a single component of an at least trifunctional polycarboxylic acid and a monoalcohol or a single component of an at least trifunctional polyol and a monocarboxylic acid as starting materials.

But also di- or tri-alkyl esters of tricarboxylic acids and tri- or tetra-alkyl esters of tetracarboxylic acids; di- or tri-esters of aliphatic carboxylic acids of triols and tri- or tetra-esters of aliphatic carboxylic acids of tetraols; monohydroxy Di- or trialkyl esters of dicarboxylic acids or dihydroxymonocarboxylic acids can also be used. In these compounds, during the formation of the basic polyester, only the alkyl ester group of monocarboxylic acid or monoalcohol or the alkyl ether of monoalcohol is retained as an alkyl side chain in the basic polyester, and the other alkyl ester groups are retained by conventional methods. separated.

In addition, glycidyl esters of monocarboxylic acids can also be used.

Also very preferred are saturated polyester-forming starting materials, ie saturated diols and saturated dicarboxylic acids, saturated tricarboxylic acid esters or optionally saturated tricarboxylic acids, saturated triols such as glycerin and especially glycidyl esters. However, starting materials with relatively small amounts of unsaturated groups, up to about 2 mol %, can also be used, such as maleic anhydride or fumaric acid.

Polyester-forming starting materials for forming the main chain of the basic polyester are typically trivalent or higher valences or divalent ones, and specific starting materials include the following polyesters of divalent or higher valences: Forming starting materials are preferred.

1) Dicarboxylic acids; terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, isophthalic acid, phthalic acid and 2 to 12 carbon atoms
and their polyester-forming derivatives, such as azelaic acid, sebacic acid and dodecanoic acid.

■) Trivalent or higher polycarboxylic acids; trimellitic acid, trimesic acid, hemeritic acid, pyromellitic acid and their polyester-forming derivatives, and very preferably trimellitic anhydride and trimellitic acid monoalkyl esters, dialkyl esters and trimellitic acid Alkyl ester.

ui) Diols: Aliphatic diols with 2 to 6 carbon atoms, such as monoethylene glycol or hexanediol, and ether diols, such as diethylene glycol, triethylene glycol to polyether glycols with a molecular weight of 1000.

iv) Trivalent or higher polyols; glycerin, pentaerythritol and very preferably trimethylolpropane, trimethylolethane, di-trimethylolpropane ether and their esters and ethers, monocarboxylic acids, especially the so-called Versatic acids. ure ) glycidyl ester.

■) Mono- and dihydroxycarboxylic acids; hydroxysuccinic acid (malic acid).

The alkyl side chains in the basic polyester are directly bonded to the main chain via ester or ether bonds,
Specifically, a functional group that does not participate in the formation of the polyester main chain in tricarboxylic acid, tetracarboxylic acid, triol, or tetraol in the ester constituent unit, that is, a carboxyl group or a hydroxyl group, is added to the main chain. When the functional group in the main chain is a carboxyl group, the alkyl side chain is a monoalkanol residue,
When the functional group in the main chain is a hydroxyl group, it is a monocarboxylic acid residue or a monoalkanol residue.

For the formation of alkyl side chains, preferably the branched alkanol in the form of its ester or as a single component is
or a preferably branched aliphatic monocarboxylic acid having 4 to 36 carbon atoms, preferably 4 to 18 carbon atoms, in the form of its ester or as a single component, or alternatively the above-mentioned trihydric or higher polyols, polyhydric Preference is given to using di- or optionally diesters or mono- or optionally diethers of carboxylic or hydroxycarboxylic acids. Highly preferred starting materials are branched chain alkanols such as 2-ethylhexanol or t-butanol;
- branched aliphatic monocarboxylic acids such as ethylhexanoic acid, isononanoic acid, or α,α-dialkyl monocarboxylic acids, such as versatic acid having 9 to 11 carbon atoms.

Among the above starting materials, trimellitic acid mono-2-ethylhexyl ester or a mixture of trimellitic anhydride and 2-ethylhexanol is extremely preferred as having a carboxyl group constituting an ester constituent unit; Trimethylolpropane monoester, particularly its mono-2-ethylhexane ester, is extremely preferred as having a hydroxyl group constituting the unit.

In order to produce the basic polyester, for example, JP-A-62-
11722, and there are the following two methods.

The first method involves mixing a trivalent or higher valent polycarboxylic acid, its anhydride, or its ester-forming derivative, especially a methyl ester or a trivalent or higher polyol, with a monocarboxylic acid and/or a monoalkanol before forming a polyester main chain. This method uses a monoester or optionally a diester obtained by reacting a monoester or a monoether or optionally a diether, and is more advantageous than the second method described below. This method is
It is also particularly advantageous for versatic acid and branched alcohols, which are difficult to esterify, such as 2-ethylhexanol.

The incorporation of versatic acid is also possible by using the corresponding commercially available glycidyl esters, in particular by reacting them first with a dicarboxylic acid, for example an aliphatic dicarboxylic acid, and in a second step with an aromatic dicarboxylic anhydride. Other polyester raw materials can then be added.

Trimethylolpropane can be used advantageously, especially in its mono- or tri-ester form.

The second method is a method in which a monocarboxylic acid and/or a monoalkanol is present during esterification and polyester formation, and in this case, it is preferable to have an excess amount of a monofunctional side chain forming compound present. .

Esterification and polyester formation can be facilitated by catalysts. Furthermore, the statistical distribution of alkyl side chains can optionally be promoted by lowering the esterification temperature and increasing the esterification time. The temperature during esterification and polyester formation is generally from 180 to 260' C1, especially from 200 to 240
It is preferable to set it to °C.

At the end of the polycondensation, a pressure of 10 to 20 mbar is particularly preferred.

It is possible to use monoalkanols together with tricarboxylic acids or triols and aliphatic monocarboxylic acids together with triols in the polycondensation and to thus generate alkyl side chains during the polycondensation. But it's not advantageous.

An excess amount of diols and triols or their esters or derivatives is used relative to dicarboxylic acids and tricarboxylic acids or their esters or derivatives, and as the polycondensation progresses, the hydroxyl value is from 10 to 100 and the acid value is from 5 to 5, especially from 3 or less. It is preferably used until it becomes 1 or less.

Next, a method for imparting (meth)acryloyloxy groups to the basic polyester obtained as described above will be described.

The hydroxyl groups of the basic polyester are replaced with (meth)acryloyloxy groups by reaction with (meth)acrylate compounds. The (meth)acrylate compound used in this reaction is not limited in type as long as it has a functional group that can react with a hydroxyl group or a carboxyl group as described below.

The simplest compounds that can be reacted with hydroxyl groups include (meth)acrylic acid or (meth)acrylic chloride or (meth)acrylic anhydride. In addition, as compounds having a functional group that can be reacted with a hydroxyl group, there are the following.

■ Isocyanate alkyl (meth)acrylate (the alkyl group is an ethyl or propyl group).

■ Isocyanate prepolymer of di-, tri-isocyanate, poly-isocyanate or polyester or polyether with low molecular weight and hydroxyalkyl (
Addition products with meth)acrylates.

Isocyanates include toluylene diisocyanate, methylene diphenyl-4-14''-diisocyanate, hexamethylene diisocyanate, benzyl-1,4
- Diisocyanates such as diisopropylisocyanate and isophorone diisocyanate and triisocyanates which can be reacted with 2 moles of hydroxyalkyl acrylate can also be used.

The above-mentioned addition product having isocyanate groups and (meth)acryloyloxy groups in a ratio of 1:1 contains about an equivalent amount of hydroxyalkyl ( meth)acrylate.

Isocyanate prepolymers, in preformed form,
For example, Desmozur (Des+5odur) P F [
manufactured by Bayer AG], prepared, for example, from triethylene glycol by reaction with the diisocyanate, or prepared, for example, from 3 or 5 molecules of 2 or 3 mol of ethylene glycol and 1 or 2 mol of dicarboxylic acid. The addition product can be formed by reacting the reaction product with one of the diisocyanates and reacting the isocyanate prepolymer thus obtained with a hydroxyalkyl acrylate.

■Methyl-acrylamide glycolate-methyl ether.

Methyl-acrylamide glycolate-methyl ether or the corresponding acrylamide glycolate-methyl ether can also be used.

In addition to directly reacting the hydroxyl groups of the basic polyester with the (meth)acrylate compound as described above, as shown below, the hydroxyl groups are reacted with a compound having a reactive functional group to impart carboxyl groups to the basic polyester. ,
Contains a functional group that is reactive with carboxyl groups (meta)
It is also possible to impart (meth)acryloyloxy groups to the basic polyester by reacting with an acrylate compound.

(2) That is, a carboxyl group is formed by reacting the hydroxyl group of the basic polyester with an aliphatic or aromatic dicarboxylic acid, tricarboxylic acid, or their anhydride, such as phthalic anhydride, and then this carboxyl group and glycidyl (meth)acrylate. are reacted, preferably by adding a polymerization inhibitor.

The preferable reaction ratio of the compounds (1) to (3) above is 1.0 to 11 equivalents per equivalent of the hydroxyl group of the basic polyester or the carboxyl group imparted to the basic polyester, for example, at a temperature of 60 to 150°C and a pressure of 300 mbar. The reaction is carried out at normal pressure and with exclusion of air moisture.

The compounds (1) to (2) above may be used alone or in combination of two or more, and the reaction with the hydroxyl groups of the basic polyester is preferably carried out on 10 to 90% of the hydroxyl groups of the basic polyester.

Among the hydroxyl groups of the basic polyester, those that are not replaced with (meth)acryloyloxy groups by the reaction with the above-mentioned (meth)acrylate compound can be allowed to exist as they are, or can be reacted to crosslink the basic polyester. It can be reacted with organic or crosslinking compounds such as isocyanates, melamine or benzoguanamine resins, epoxides or silane esters.

As described above, the various properties of the basic polyester with a (meth)acryloyloxy group added to the molecular end are related to the properties of the basic polyester as a raw material, and Tg
is less than O'C - 60°C or more; amorphous product; weight average molecular weight is 1000-20000, more preferably 200
0-15000i hydroxyl value is 1-90 KOHmg/g
It is preferable to satisfy the following.

Commercially available products of component (A) include Dynacol A-3652T and Dynacol A-3652T, commercially available from Huls.
3652, Dynacol A-1530, Dynacol A
-1550, Dynacol A-2330, Dynacol A-3151, Dynacol A-3251 and Dynacol A-3351.

The preferred blending ratio of component (A) is 100 parts by weight (hereinafter simply referred to as "parts") of the total amount of components [A], CB), and [C).
The amount is 30 to 90 parts, more preferably 40 to 80 parts, and still more preferably 50 to 70 parts.

[B] component and [B] component are monofunctional acrylates represented by the following formula.

CH, -CHC0CHICHCH! O-R1 00H In the above formula, R1 represents an alkyl group having 4 to 18 carbon atoms. When the number of carbon atoms in R1 is 3 or less, the cured product obtained by the composition of the present invention becomes hard, and when the number of carbon atoms is 19 or more, the cohesive force of the composition of the present invention is lost, making it brittle, and any In some cases, the adhesive properties cannot be exhibited.

This CB] component can be obtained by various reactions, for example, it can be easily obtained by an addition reaction between an alkyl glycidyl ether and acrylic acid.

Any alkyl glycidyl ether may be used as long as the alkyl group has 4 to 18 carbon atoms, such as 2-ethyl butyl glycidyl ether, 2-ethylhexyl glycidyl ether (commercially available products such as Wilmington Chemical Co., Ltd. rMK-116 manufactured by the company)
, 2-methylpentyl glycidyl ether, 4-methyl-2-pentyl glycidyl ether, 2-hebutyl glycidyl ether, 3-hebutyl glycidyl ether, dodecane glycidyl ether, tetradecane glycidyl ether (a mixture of this compound and dodecane glycidyl ether) Commercially available products include, for example, rWC-8J manufactured by Wilmington Chemical Co.), butyl glycidyl ether (commercially available products include, for example, rWC-8J manufactured by Yokkaichi Gosei Co., Ltd.).
There are those having a linear or branched alkyl group, such as DY-BP), hexadecane glycidyl ether, and octadecane glycidyl ether.

The charging ratio when reacting acrylic acid and glycidyl ether may be according to conventional techniques, for example, 0.9 to 1 mol of acrylic acid to 1 mole of glycidyl ether.
Preferably, the proportion is 1.0 mol.

The addition reaction between acrylic acid and glycidyl ether can also proceed by heating without adding a catalyst, but it is generally preferable to carry out the reaction in a reaction solvent containing a known catalyst because the reaction rate is faster.

Preferred catalysts include Lewis acid type compounds such as boron trifluoride or sulfonic acid; sulfonium salts such as para-toluenesulfonic acid or triphenylsulfonium chloride; metal hydroxides such as caustic soda, caustic potash or lithium hydroxide; triethylamine, Amines such as benzyldimethylamine or dimethylamine hydrochloride; Quaternary ammonium salts such as tetrabutylammonium bromide;
Metal halides such as tin chloride; benzenephosphonic acid,
Examples include phosphonium salts such as triphenylmethylphosphonium iotide; and organic acid salts such as sodium phthalic acid.

The amount of the catalyst used is o, oooi to 20 parts, more preferably o, oo
The range is preferably from s to 5 parts.

Examples of solvents include ketones such as dipropyl ketone,
Aromatic hydrocarbons such as henzene, toluene, and petroleum; Esters such as ethyl acetate, butyl acetate, and butyl lactate; Alcohols such as ethyl alcohol and diacetone alcohol; Cellosolves such as isopropyl cellosolve and celloacetate; acetyl ethyl Ethers such as ether and tetraethylene glycol diethyl ether: one or more selected from acetoacetic acid and the like can be used.

The amount of solvent used is 30% of the total reactants.
It is preferable that the content be in the range of ~80% by weight (hereinafter, % represents weight%).

Also, if necessary, to prevent gelation during the reaction,
Compounds such as phenols and quinones can be used as polymerization inhibitors. Furthermore, when these polymerization inhibitors are added after the reaction, they also have the effect of preventing the polymer from gelling during storage.

Specific examples of preferable polymerization inhibitors include phenols such as hydroquinone, hydroquinone 7-methyl ether, t-butylhydroquinone, catechol, and t-butylcatechol, quinones such as benzoquinone, naphthoquinone, and diphenylbenzoquinone, phenothiazine, and copper salts. be.

The amount of these polymerization inhibitors used is 0.00% relative to component [B].
It is preferable to set it in the range of 0001 to 0.3%.

The [B] component and its preferred blending ratio are 5 to 95 parts, more preferably 10 to 40 parts, based on the total of 1100 parts of the [A], [B] and [C] components.

It is a monofunctional acrylate represented by the following formula, and has the effect of improving adhesiveness and cohesive force with metals, glass, etc.

CH, -CHCoXH 1 (In the above formula, X is a divalent group represented by the following (1) or (2).) (1) iCCH2), GO).

1 (In the above formula, m=2-7, !=1-7.

) (2)-CHlCHOC-Y-C0 111] R200 (In the above formula, R2 is hydrogen or a methyl group, and Y is a dibasic acid residue.) A monofunctional compound represented by the above formula (1) I in acrylate
When 1 is 0, there is a problem with odor, and when 1 is greater than 7, the cured composition of the present invention loses cohesive force and becomes dangerous.

The monofunctional acrylate represented by the above formula (1) may be used alone or in combination of two or more. A specific example of a monofunctional acrylate corresponding to this is a compound obtained by ring-opening addition polymerization of a lactone to acrylic acid, and
An example of this is shown in Publication No. 6, and an example of a commercially available product is "Aronixt 5300J (trade name, manufactured by Toagosei Chemical Industry Co., Ltd., m = 5, I = 1 to 5, average value of ■ = 1.8
). Another example of the above-mentioned monofunctional acrylate is an addition polymer of acrylic acid, which is commercially available as "Aronixt 5600" (trade name, manufactured by Toagosei Kagaku Kogyo Co., Ltd., m = 2.1 = 1 to 7, average value of l = 1.4'').

The compound represented by the above formula (2) is an acrylate obtained by, for example, a reaction between a hydroxyl group-containing acrylate and a dibasic acid anhydride, and specific examples of Y include the following groups.

-CH, --CH, -CH, -CH=CH Above (2)
Specific examples of monofunctional (meth)acrylates represented by the formula include compounds listed in Table 1 of Japanese Patent Publication No. 52-7367, namely, succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyisopropyl ester , monoacryloyloxyethyl maleate, monoacryloyloxyisopropyl maleate, monoacryloyloxyethyl hexahydrophthalate, monoacryloyloxyethyl tetrahydrophthalate, monoacryloyloxyethyl phthalate, monoacryloyloxyisopropyl phthalate Examples include ester ζ-himic acid monoacryloyloxyethyl ester.

Component [C] and its preferred blending ratio are 5 to 60 parts, more preferably 10 to 40 parts, per 100 parts of the total amount of components [A], [B] and [C].

<Copolymerizable monomer> In the present invention, in addition to the above-mentioned components, a monomer copolymerizable with these components can be further used in combination. By appropriately using these copolymerizable monomers in combination, the properties required in various uses can be more fully satisfied.

As the copolymerizable monomer, for example, the monofunctional (meth)acrylate shown below can be used.

■) (Meth)acrylates of alkylene oxide polyadducts of phenol or alkylphenols such as ethylene oxide and propylene oxide. For example, polyethylene glycol monophenyl ether
(meth)acrylate, ・Polyethylene glycol monononylphenyl ether mono(meth)acrylate, ・Polypropylene glycol monononylphenyl ether mono(meth)acrylate.

2) A (meth)acrylate obtained by ring-opening polyaddition of a lactone to a hydroxyl group-containing (meth)acrylate, such as a 6-hexanolide polyadduct of 2-hydroxyethyl (meth)acrylate.

3) (meth)acrylates of other monofunctional alcohols, such as dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryloxyethyl (meth)acrylate ((meth)acrylate of ethylene oxide adduct of tetrahydrofurfuryl alcohol), - (Meth)acrylate of 6-hexanolide polyadduct of tetrahydrofurfuryl alcohol.

The molecular weight of the monofunctional (meth)acrylate is 200-
A range of 1000 is desirable. Molecular weight is 200
If the molecular weight is less than 100, problems will occur due to odor due to the high vapor pressure of the monofunctional (meth)acrylate;
If it exceeds 0, the viscosity of the adhesive increases and the concentration of (meth)acryloyl groups per molecule decreases, resulting in insufficient polymerizability.

The copolymerized amount of the copolymerizable monomer is preferably in the range of 0 to 50%, more preferably 0 to 40%, based on the total monomers.

Other components> The composition of the present invention essentially does not require a solvent, but includes, for example, ketones such as methyl ethyl ketone and methyl isobutytorketone; acetate esters such as ethyl acetate and butyl acetate; benzene. It is also possible to use the composition of the present invention after diluting it with other commonly used organic solvents such as aromatic hydrocarbons such as toluene and xylene.

In addition, other polymers soluble in the composition of the present invention can be blended within a range that does not impair the adhesive properties. Specific examples of the polymers include (meth)acrylic acid ester, styrene, vinyl acetate, Examples include (meth)acrylic acid, and polymers obtained by copolymerizing two or more monomers constituting these polymers may also be used.

The preferred blending ratio of these polymers or copolymers is 0 to 50% by weight in the total weight of the composition of the present invention;
More preferably, the range is 0 to 40%.

Furthermore, various additives conventionally used in the field of adhesives, such as leveling agents, antifoaming agents, tackifiers, and flow inhibitors, can also be incorporated into the composition of the present invention. The amounts of these additives may be determined according to conventional techniques.

The composition of the present invention can be easily obtained by mixing the above components in any order.

Method for Curing the Composition> In order to cure the composition of the present invention, it is sufficient to irradiate it with active energy rays, and the active energy rays include UV,
In addition to EB, ionizing radiation such as T-rays is also included, and the irradiation conditions may be determined according to conventional methods.

Further, in order to further accelerate curing, a curing accelerator may be included.

When curing by UV irradiation, it is desirable to use a photoinitiator, and specific examples of preferred photoinitiators include:
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether; benzyl, diacetyl, benzylacetyl, methylanthraquinone, acetophenone, benzophenone, 2-hydroxy-2-methylpropiophenone carbonyl compounds such as; sulfur compounds such as diphenyldisulfisode and dithiol rubamate; naphthalene compounds such as α-chloromethylnaphthalene; metal salts such as anthracene and iron chloride. The preferred amount of the above initiator is 0.01 to 20% by weight based on the composition.
, more preferably 0.1 to 10% by weight.

On the other hand, when irradiation with ionizing radiation such as EB or T-rays is used as a curing means, curing occurs quickly without using a photoinitiator, so there is no need to use a photoinitiator.

[Example〕 The present invention will be explained in more detail below using Examples.

Examples 1 to 10 In each example, various types of Dynacol A commercially available from Hüls were used as component (A). Their weight average molecular weights were measured as follows and the results are shown in Table 1.

Column: TSK Gel GMIIx2 (polystyrene equivalent) manufactured by Tosoh Corporation Solvent: Tetrahydrofuran Flow rate: 1, 1 ml/min Model: HLC802A manufactured by Tosoh Corporation The acid value and hydroxyl value of component (A) are also shown in Table 1.

A mixture of component (A), component [B] and/or component [C] having the composition shown in Table 2 was prepared, and each mixture was placed on a polyethylene terephthalate film with a thickness of about 25 μm.
A pressure-sensitive adhesive sheet was prepared by applying the adhesive to a thickness of m at room temperature and polymerizing it by irradiating it with EB or UV under the following conditions. Their respective physical property values are as shown in Table 3.

EB irradiation device: "Electro Curtain" manufactured by ES1 Acceleration voltage: 1
70 KV Irradiation dose: 5 Mr ad Oxygen concentration in the atmosphere: 100-200 ppmU ■ Irradiation U ■ Irradiation device: Ushio Inc. "Unicure 4000" Lamp: 80 W/cm, ozone type high pressure mercury lamp (distance of 10 cm from the object to be irradiated) Reflector: Light condensing type (light condensed on the conveyor) Conveyor speed: 10 m/mm Number of irradiations: 5 times 2-hydroxy-
Contains 5 parts of 2-methylpropiophenone.

Various physical properties of the pressure-sensitive adhesive sheet were measured in a room at a temperature of 23° C. and a humidity of 65% by the following method.

The adhesive pressure-sensitive adhesive sheet was pressure-bonded to a stainless steel plate and a polyethylene plate, and a 180° peel test was conducted in accordance with JIS-6854.

Holding force: The pressure-sensitive adhesive sheet is crimped onto an aluminum plate, and held horizontally in an oven at 40°C with the crimped surface of the pressure-sensitive adhesive sheet facing downward.
A weight was attached so that a load of kg was applied, and the time until the pressure-sensitive adhesive sheet peeled off from the aluminum plate was measured. Those that did not fall off even after 180 minutes were labeled as NC.

Pole tank: A pressure sensitive adhesive sheet was attached to a slope with an angle of 30' with the adhesive coated side facing up, and measurements were taken according to JIS-20237.

In addition, the coating suitability was compared when component [A] and a certain Dynacol A3151 alone and the composition of Example 2 were coated at room temperature at a line speed of 50 m/min using a reverse roll coater. As a result, Dynacol A31
When the composition of Example 2 was used alone, the degree of misting was large, and the appearance of the coated surface was rough and the film thickness was uneven, whereas when the composition of Example 2 was used, there was no misting. There is no tinging at all, and the coated surface has a good appearance (c)
Effects of the Invention The composition of the present invention essentially solves various problems caused by solvents and low-boiling acrylic monomers, namely, hazards to workers, fire hazards, environmental pollution, odor control, and drying speed. ,
This eliminates the waste of resources (solvent), etc., and furthermore, the physical properties as an adhesive are significantly improved, and it is particularly prized as a composition for pressure-sensitive adhesives.

Claims (1)

[Scope of Claims] An active energy ray-curable composition characterized by containing the following components [A] and [B] and/or the following components [C]. [A]: A comb-shaped polyester having a hydroxyl group and a (meth)acryloyloxy group at the molecular terminal, and an alkyl side chain directly bonded to the main chain via an ester bond or an ether bond. [B]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R^1 represents an alkyl group with 4 to 18 carbon atoms.) [C]: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, X is a divalent group shown in the following (1) or (2).) (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the above formula, m = 2 ~ 7, l = 1 to 7.) (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above formula, R^2 is hydrogen or a methyl group, and Y is a dibasic acid residue.)