JPH02284978A - Photo-setting adhesive composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, consisting essentially of a liquid polymer, prepared by hydrogenating a specific liquid polyisoprene and having specified photopolymerizable groups at both terminals and excellent in heat, water resistance, etc. CONSTITUTION:The objective composition obtained by hydrogenating >=50%, (preferably >=80%) unsaturated bonds in a liquid polyisoprene, prepared by radially polymerizing isoprene monomer, etc., using an azo compound, etc., as a polymerization initiator, etc., and having 700-7000 (preferably 1000-5000) number-average molecular weight to provide a hydrogenated liquid polyisoprene, mixing and reacting the above-mentioned hydrogenated polyisoprene with an organic polyisocyanate compound, providing a prepolymer, reacting the resultant prepolymer with an ester having a photopolymerizable group, such as acryloyl, methacryloyl, acrylamide or methacrylamide, affording a hydrogenated liquid polyisoprene having the photopolymerizable groups at both terminals and further blending the above-mentioned hydrogenated polyisoprene having the photopolymerizable groups as an essential component with benzophene, toluene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a light-curable composition comprising:
The present invention relates to a novel adhesive composition comprising a liquid polymer, the cured product of which has excellent heat resistance, weather resistance, water resistance, and adhesive performance.

[Conventional technology]

Photocurable adhesives have a crosslinking agent with good fluidity, and are quickly cured by light and exhibit adhesive performance.
2. Description of the Related Art Photocurable adhesives made of a mixture of liquid polybutadiene and (meth)acrylic acid ester are known. Although this adhesive exhibits excellent water resistance and adhesive properties, it has the drawback of poor heat resistance and weather resistance due to the presence of unsaturated bonds in the main chain. Moreover, since polybutadiene is nonpolar, its compatibility with (meth)acrylic acid ester is insufficient, and the mechanical strength of the cured product is not necessarily sufficient.

On the other hand, for the purpose of improving compatibility with (meth)acrylic acid ester, photocurable material using maleated I-lipta-diene, which has maleic anhydride added to its molecular chain, instead of liquid polybuta-diene. Adhesives are known, but when they are used as adhesives, sufficient adhesive strength cannot be obtained, and maleated polybutadiene has problems such as silting and coloring during its production.

[Problem to be solved by the invention]

The present invention is a composition of a type that is cured by light,
The object of the present invention is to provide a novel adhesive composition composed of a liquid polymer, the cured product of which has excellent heat resistance, weather resistance, water resistance, and adhesive performance.

[Means to solve the problem]

That is, in the present invention, the number average molecular number is 700 to 7.00.
A liquid polyisoprene in which 50% or more of the unsaturated bonds in the liquid polyisoprene of No. The present invention relates to a photocurable adhesive composition containing coalescence as an essential component.

In the present invention, liquid /IJ inprene having a number average molecular t of 700 to 7,000 is used. When the number average molecular weight is less than 500, the adhesive composition obtained using the hydrogenated product having the photopolymerizable group does not have good rubber elasticity. In addition, if it exceeds 7,000, the hydrogenated liquid polyimprene will no longer exhibit good fluidity.
This is undesirable because the operability in producing the adhesive composition becomes significantly worse. From this point of view, it is necessary that the number average molecule t be within the above range, particularly preferably from 1,000 to s, ooo.

The hydrogenated liquid polyisoprene must have photopolymerizable groups at both ends. When only one end has a photopolymerizable group, sufficient crosslinking cannot be achieved and the coercive properties become insufficient. This photopolymerizable group may be present not only at both ends of the molecular chain but also within the molecular chain.

Examples of the photopolymerizable group include an acryloyl group, 2-methacryloyl group, an acrylamide group, and a methacrylamide group.

Such liquid polyimprene can be obtained by a known method. For example, a liquid polyinoprene with hydroxyl groups removed at both terminals 1 is polymerized and the hydrogenated product is obtained by passing through a hydrogen sieve.Then, a difunctional a-organic incyanate compound is reacted to remove 2Cf 7 cyanate groups at both ends. A method of obtaining stagnation liquid polyisoprene (rupolymer) and further reacting it with (meme)acrylic ester having a hydroxyl group,
There is.

In addition, by reacting a hydrogenated product of liquid polyisoprene having hydroxyl groups at both ends with inocyanate alkylene acrylate or inocyanate alkylene methacrylate, liquid polyisoprene having photopolymerizable groups at both ends and four ends can be prepared. A method for obtaining a hydrogenated product of water is also mentioned.

Here, liquid polyimprene having hydroxyl groups at both ends can be prepared by, for example, replacing imprene monomer with hydrogen peroxide, an azo compound having a hydroxyl group (for example, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl )-propionamide] etc.) or hydroxyl group-containing
For example, using cyclohexanone, f-oxide, etc.) as a polymerization initiator, the amount of
It can be obtained by radical polymerization using a molar ratio within the range.

t, Inglene monomer 100 parts by weight, Naphthalene tholithium, r! After anionic polymerization using 0.1 to 5 parts by weight of the imprene monomer as a polymerization initiator such as l-zolithiohexylbenzene.

Hydroxyl group-containing liquid I reinprene can also be obtained by adding 1 to 300 moles of ethylene oxide, propylene oxide, etc. to 1 mole of the l&initiator.

In both radical polymerization and anionic polymerization, it is necessary to use a solvent that is inert to the catalyst.

Examples of solvents for radical polymerization include ethanol,
Alcohols such as telonofnor, hexane.

Aliphatic and alicyclic hydrocarbons such as heptane and cyclohexane, aromatic hydrocarbons such as benzene and toluene, and the like are used. Examples of solvents for anionic polymerization include aliphatic solvents such as pentane and cyclohexane.

Alicyclic hydrocarbons, aromatic hydrocarbons such as benzene, toluene, etc. are used.

tVi of the solvent can be determined arbitrarily, but 80% of the entire polymerization system
It is desirable to do the following. There are no particular restrictions on the conditions for polymerization, but in any polymerization method, the temperature is 0 to 200°C,
1-10. This is done within a range of about 0 hours.

By the above method, a liquid polyimprene containing hydroxyl groups at both ends of the molecular chain can be obtained.

In the present invention, the hydroxyl group-containing liquid polyimprene is used after being hydrogenated. At this time, 50 or more unsaturated bonds in the polymer need to be hydrogenated.

When the hydrogenation rate is lower than 50, the adhesive obtained using the hydrogenation rate has a problem of deterioration due to heat or light due to unsaturated bonds. From these points of view, the hydrogenation rate must be 50 or more, preferably 80 or more.

Hydrogenation of the hydroxyl group-containing liquid polyimprene can be carried out using a known method. For example, a method of carrying out catalytic hydrogenation using a Ziegler type homogeneous catalyst or a solid heterogeneous catalyst is adopted.

When using a homogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, benzene, and toluene.

Using aromatic hydrocarbons such as xylene as a solvent, at room temperature to 20℃
The hydrogenation reaction is carried out at a reaction temperature of 0° C. and a hydrogen pressure of from normal pressure to 100 kl/ls2. As a homogeneous catalyst, a Ziegler catalyst made of a combination of a transition metal organic compound and an alkali compound such as aluminum, an alkaline earth metal, or an alkali metal is used to the extent of 0.01 to 0.1 mole per unsaturated bond in the polymer. However, the reaction is usually 1-2
It will be finished in 4 hours.

When using a heterogeneous catalyst, saturated hydrocarbons such as hexane and cyclohexane, benzene, and toluene.

Aromatic hydrocarbons such as xylene, diethyl ether.

THF, ethers such as sooxane, ethanol.

Using an alcohol such as inglono-4-nol or a mixture thereof as a solvent, at a reaction temperature of usually m to 200 tl,
The hydrogenation reaction is carried out under hydrogen pressure of normal pressure to 100 kWcm2. Nickel is a heterogeneous catalyst.

・Metals such as I-radium, ruthenium, platinum, etc. are used alone or supported on a carrier such as silica, quartzite, alumina, activated carbon, etc., and the amount is 0.5 to 10% relative to the polymer IT.
The reaction is usually completed in 1 to 48 hours.

In the present invention, the liquid polymer (prepolymer) in which the hydroxyl groups at both ends of the hydrogenated polymer are converted into incyanate groups is
It can be obtained by mixing a hydrogenated product of liquid I-reinprene containing a hydroxyl group with an organic polyinsyanate compound, and, depending on the case, heating the mixture and reacting the mixture. The difunctional organic preincyanate compounds used here include tolylenezoincyanate, diphenylmethane diincyanate, 1,5-naphthalenezoincyanate, hexamethylene diincyanate, inphorone diincyanate, and knock-a hexylmethanezoin. Examples include cyanate. The amount of the organic polyin 7-anate compound is 1 to 50 parts by weight per 100 parts by weight of the hydrogenated liquid imprene polymer containing hydroxyl groups.

Hydroxyl groups (O
H) and the incyanate group (NCO) in the organic polyincyanate compound are used in a molar ratio of NCO10H=1,0. Reaction temperature is room temperature to 150℃, reaction time is 0.1
It is carried out for a period of ~20 hours. At this time, it is also possible to use compounds such as tin and lead as catalysts.

In the present invention, the hydrogenated product of liquid polyimprene having photopolymerizable groups at both ends can be prepared, for example, by mixing a prepolymer and a (meth)acrylic acid ester having a hydroxyl group, and in some cases heating and mixing to cause a reaction. More can be obtained.

As the (meth)acrylic acid ester having a hydroxyl group used here, 2-hydroxyethyl 7! 7 Leh
) (HEA), 2-hydroxyglopylacrylate (HPA), dipentaerythritol monohydroxyacrylate, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxyethyl methacrylate, and the like.

The amount of fecal amount of (meth)acrylic acid ester having a hydroxyl group is! Repolymer 100]ii 0, 1 to 1O for a part
Parts by weight. At least one type of (meth)acrylic ester selected from the above is used as the (meth)acrylic ester having a hydroxyl group.
H) is used in a molar ratio of NC010H=1.0. The reaction temperature ranges from room temperature to 150°C, and the reaction time ranges from 0.1 to 20 hours.

At this time, unreacted hexamer can be removed by washing with a solvent, drying under reduced pressure, etc., but does not necessarily have to be removed. Furthermore, it is also possible to add a polymerization inhibitor or a catalyst. Examples of the polymerization inhibitor include p-benzoquinone, hydroquinone,
Nitronphenol.

Examples of the catalyst include aminophenol, dibutyltin dilaurate, stannath octoate,
Triethylenediamine, triethylamine, etc. can be mentioned.

By the method described above, a hydrogenated liquid polyisoprene having photopolymerizable groups at both ends can be produced.

Since the hydrogenated product has photopolymerizable groups at both ends, it can be photopolymerized with various polymerization initiators, such as evabenzoin, benzoin methyl ether, benzoin ethyl ether, penzoinde Q biyl ether, and benzophenone. Appropriate amount of initiator, specifically liquid 4 containing photopolymerizable groups at both ends.
0.5 to 1 per 100 parts by weight of Reimprene hydrogenated product
It may be added in a range of 0 parts by weight. Further, a radical polymerization initiator such as azobisinbutyronitrile, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, etc. may be used in combination with the photopolymerization initiator.

A composition containing a hydrogenated liquid polyisoprene containing photopolymerizable groups at both terminals as an essential component can be cured by irradiation with ultraviolet rays, electron beams, etc. At this time, auxiliary components may be added as appropriate.

Examples of the above-mentioned auxiliary components include monofunctional or polyfunctional photopolymerizable monomers, photopolymerizable prepolymers, photopolymerizable diluents, and fillers such as clay and silica.

Antiaging agents such as phenolic and amine type, tackifying resins such as rosin type and terpene type, and naphthene type.

Paraffinic and aromatic process oils, as well as
Examples include plasticizers such as dioctyl phthalate and so-octyl adipate. Here, specific examples of the monofunctional or polyfunctional photopolymerizable monomer, photopolymerizable prepolymer, and photopolymerizable diluent include inbutyl acrylate, 2-ethoxyethyl acrylate, and tetrahydrofurfuryl acrylate.

Monofunctional (meth)acrylic acid esters such as lauryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 1,4-butanediol diacrylate, nopentaerythritol monohydroxyacrylate, ethylene glycol zomequa acrylate, trimethylol glono Examples include polyfunctional (meth)acrylates such as matrix methacrylate. The amount of these auxiliary components to be added is not limited as long as it does not impair the purpose and effect of the present invention, and is determined as appropriate; , 0~
It is 200 parts by weight.

The cured product obtained by using the liquid polymer of the present invention and irradiating it with ultraviolet rays using a low-pressure mercury lamp or high-pressure mercury lamp as a light source, or electron beams using an electron beam accelerator as a radiation source has good heat resistance, weather resistance, and water resistance. It has excellent adhesion performance. EXAMPLES Hereinafter, the present invention will be explained in more detail according to examples, but the present invention is not limited to the following examples unless it exceeds the spirit thereof.

Example 1 Hydroxyl group-containing liquid polyisoprene (Mn
= 2,600, OH number = 45.3 Fn97i
100 grams of reduced nickel, 10 grams of reduced nickel, 35% nickel supported on nickel, 200 grams of 7 chlorohexane as a reaction solvent, and when the temperature was raised to 150°C, high purity hydrogen gas was supplied to the autoclave. The hydrogenation reaction was carried out while maintaining the internal pressure of the system at 50 to 6. The reaction hydrogenated product was taken out, the υ catalyst was removed by filtration, and the solvent was distilled off to obtain a hydrogenated product (I) of liquid polyimprene containing hydroxyl groups. The hydrogenation rate of hydrogenated product (I) was 94% as a result of iodine value measurement. Next, this hydrogenated product (1) 100! I, inphoron diincyanate 8.9, lit (NGOloH=1.
0) and heated to 100℃ while blowing nitrogen gas.
The mixture was reacted for 5 hours to obtain a hydrogenated liquid polyimprene containing incyanate groups at both terminals (prepolymer (I)).

This prepolyff-(1)l OOFK, 2-hydroxyethyl acrylate (HEA) 9.4 Il, hydroquinone monoethyl ether (M positive Q) 0.05. l
After adding it, the mixture was reacted at 120° C. for 5 hours to obtain a hydrogenated liquid polyimprene containing acryloyl groups at both ends (Acryle-1). A pressure-sensitive adhesive composition was obtained using acrylate (1) under the formulation and curing conditions shown in Table 1. The heat resistance, adhesive performance, holding power, and adhesive strength of these adhesives were measured, and the results are summarized in Table 1.

Here, in the heat resistance test in Table 1, the cured product was heated in an open gear at 120° C. for one week and changes in the state were examined. Adhesive performance and holding power at room temperature were measured according to JIS-20237. In addition, the adhesive strength was measured according to the method of JIS-20237 also when the adherends KPE and PP plates were used.

Example 2 In an autoclave with a capacity of 11, an anionic polymerization initiation catalyst consisting of naphthalene/sodium was used.
A liquid polyimprene containing hydroxyl groups at both terminals (M+
1 = 4,500, OH value = 23.69', 110
0 grams, nickel content 50 in Raney nickel lO duram
%) and 200 g of heptane as a reaction solvent were charged, and when the temperature was raised to 150°C, high purity hydrogen gas was supplied to the autoclave, and the hydrogenation reaction was carried out while maintaining the system internal pressure at 50ψ-.

The hydrogenated product was removed from the reaction, the catalyst was removed by filtration, and the solvent was distilled off to obtain a hydrogenated product ('') of liquid polyisoprene containing hydroxyl groups.The hydrogenation rate of the hydrogenated product (■) was iodine The hydrogenated product (II) was then placed in an autoclave having a capacity of 1 liter.

Incyanate ethylene methacrylate 6.5I(N
C010H=1.0), MEHQ O,05,
9 was charged and reacted at 80° C. for 5 hours while blowing nitrogen gas to obtain a hydrogenated liquid polyisoprene containing 12 methacrylate groups at both terminals (methacrylate-1).

A pressure-sensitive adhesive composition was obtained using methacrylate (1) according to the formulation and curing conditions shown in Table 1. The heat resistance, adhesive performance, holding power, and adhesive strength of these adhesives were measured, and the results are summarized in Table 1.

Comparative Example 1 A hydrogenation video was obtained in the same manner as in Example 1 except that the hydrogenation reaction was completed in a shorter time than in Example 1. The hydrogenation rate of hydrogenated product (2) was 36% as a result of iodine value measurement. This hydrogenated product (2) was prepared in the same manner as in Example 1! After obtaining repolymer (II), acrylate (In) was obtained. Acrylate (I
Using D, a pressure-sensitive adhesive composition was obtained according to the formulation and curing conditions shown in Table 1. The heat resistance, adhesive performance, holding power, and adhesive strength of these adhesives were measured, and the results are summarized in Table 1.

As shown in Table 1, the cured product of acrylate (M) with a low hydrogenation rate has excellent adhesive strength, but has poor heat resistance.

It can be seen that the holding power is significantly inferior.

Comparative Example 2 Liquid polyisoprene containing a hydroxyl group at one end (Mu = 6,200° OH value = g, OmV'g) obtained in the same manner as in Example 2 except that 0-butyllithium was used as an anionic polymerization initiation catalyst. A hydrogenated product (goods) was obtained using 100 grams in the same manner as in Example 2. The hydrogenation rate of the hydrogenated product was 96% as a result of iodine value measurement. This hydrogenated product (hydrogenated product of liquid polyinsoleno having a methacryloyl group at one end with M as in Example 2 (methacrylate (■))
) was obtained. A pressure-sensitive adhesive composition was obtained using methacrylate (II) under the formulation and curing conditions shown in Table 1. The heat resistance, adhesive performance, holding power, and adhesive strength of these adhesives were measured, and the results are summarized in Table 1.

As shown in Table 1, the cured product of a hydrogenated liquid polyimprene having a photopolymerizable methacryloyl group only at one end has insufficient curing behavior and holding power, and the adhesive/adhesive composition I can see that it is inferior as a thing.

Double Bottom Margin [Effects of the Invention] The present invention provides a novel adhesive comprising a liquid polymer that is cured by light and has excellent heat resistance, weather resistance, water resistance, and adhesive properties. Items are provided to the group.

Claims (1)

[Claims] 50% or more of the unsaturated bonds in liquid polyisoprene having a number average molecular weight of 700 to 7,000 are hydrogenated, and both terminals are selected from the group consisting of acryloyl groups, methacryloyl groups, acrylamide groups, and methacrylamide groups. A photocurable adhesive composition containing a liquid polymer having a photopolymerizable group as an essential component.