JPS5811891B2 - Setsuchiyakuseito Hozon Anteiseinis Greta - Google Patents

Description

[Detailed description of the invention] The present invention relates to photocurable compositions.

More specifically, the present invention relates to a photocurable composition with excellent adhesive properties and storage stability.

Contains an addition reaction product of an unsaturated epoxy ester obtained by the reaction of an epoxy resin and a photopolymerizable basic carboxylic acid and a polybasic carboxylic acid anhydride, a photopolymerizable monomer, and a photopolymerization initiator. A photocurable composition is described in JP-A-49-2601.

Since such photocurable compositions generally do not contain volatile organic solvents, they are very preferable from the point of view of environmental protection, and for this reason, in recent years, such compositions have been widely used in paints, printing inks, adhesives, and flexible circuits. overlays and other coating materials, printed circuit board solder resists, etching resists, metal oxide resists, and printed circuit inks.

However, the curing reaction of such photocurable compositions by irradiation with light such as ultraviolet rays or electron beam irradiation occurs rapidly in an extremely short period of time, so that distortion occurs inside the cured product.
Since it remains in the cured product, it has poor adhesion compared to conventionally used solvent-volatile or thermosetting varnishes, which often limits its use.

In order to eliminate these drawbacks, it has been proposed to add a partially amorphous saturated polyester to the composition (see Japanese Patent Application No. 49-20598).

In addition, thermoplastic resins and thermosetting resins that do not directly participate in the photocrosslinking reaction, such as polyvinyl butyral, polysulfide rubber, epoxy resin, melamine resin, polyvinyl acetate, polymethacrylate, and polyacrylate, may be added. However, these methods are not intended to modify the addition reaction product itself between an epoxy ester and a polybasic carboxylic acid anhydride; The curable composition is characterized by its viscosity,
In many cases, it is not always possible to achieve the intended purpose in terms of solubility, storage stability, adhesive effect, etc.

In the present invention, by modifying the addition reaction product itself of an epoxy ester and a polybasic carboxylic acid anhydride,
The purpose of this invention is to improve the adhesion to various substrates of cured products obtained from photocurable compositions containing it as a curable component.

This object of the present invention is to produce, as an epoxy ester, a reaction product of an epoxy resin having a urethane bond in the molecule and a photopolymerizable basic carboxylic acid, or an epoxy resin having a urethane bond in the molecule, a photopolymerizable basic carboxylic acid, and a photopolymerizable basic carboxylic acid. It has been found that this can be achieved by using a reaction product between a polybasic carboxylic acid and a polybasic carboxylic acid. It was also confirmed that the product was in good condition.

Therefore, the present invention relates to a photocurable composition with excellent adhesive properties and storage stability, and this photocurable composition comprises an epoxy resin having a urethane bond in the molecule and a photopolymerizable basic carboxylic acid. or an addition reaction between an unsaturated epoxy ester obtained by the reaction between an epoxy resin having a urethane bond in the molecule, a photopolymerizable basic carboxylic acid, and a polybasic carboxylic acid, and a polybasic carboxylic acid anhydride. It contains a product, a photopolymerizable monomer, and a photopolymerization initiator.

Epoxy resins having urethane bonds in their molecules have epoxy groups at both ends of a so-called urethane prepolymer (molecular weight approximately 300 to 8,000) derived from polyisocyanate and polyol.

For example, in the case of glycidyl ether type, it is produced as follows.

Commercially available products can also be used as such epoxy resins, for example, the following Adeka Resin (non-electronic product) can be used: Product name Epoxy equivalent Urethane content EPU
-4600~700 <40 EPU-6220<10 EPU-8240~280 13EP'[J-
10320-360 30EPU-15450
~510 Although these urethanized epoxy resins in 4 can be used alone as an epoxy resin component, commonly used epoxy resins that do not have a urethanized bond in the molecule, such as those obtained from bisphenol A and epichlorohydrin, It can be used by mixing with epoxy resins obtained by epoxidizing aliphatic or alicyclic olefins, diglycidyl ether of bisphenol A, phthalic acid dicrycidyl ester, polyalkylene glycol diglycidyl ether, and epoxy resins obtained by epoxidizing aliphatic or alicyclic olefins. Embodiments are also encompassed by the invention.

In this case, in order to achieve the purpose of improving adhesion, the urethanized epoxy resin must be used in an amount of 10% (by weight) or more of the epoxy resin component.

Photopolymerizable basic carboxylic acids that react with epoxy resin components include acrylic acid, methacrylic acid, crotonic acid,
Aliphatic unsaturated carboxylic acids such as sorbic acid, cinnamic acid,
Aromatic unsaturated carboxylic acids such as α-cyanocinnamic acid, cinnamylideneacetic acid, α-cyanocinnamylideneacetic acid, β-furfuryl acrylic acid, and mixtures thereof are used.

Along with these photopolymerizable basic carboxylic acids, polybasic carboxylic acids can also be reacted with the epoxy resin component, such as aliphatic carboxylic acids such as adipic acid and sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, Aromatic carboxylic acids such as tetrabromterephthalic acid and further alicyclic carboxylic acids such as hexahydrophthalic acid are used as polybasic carboxylic acids.

When a polybasic carboxylic acid is used, it is used in such a proportion that the molecular weight of the produced epoxy ester does not exceed about 100,000.

These carboxylic acids are generally reacted in an equivalent ratio of carboxyl groups to epoxy groups in the epoxy resin of about 0.7 to 1.5, preferably about 0.8 to 1.1.

The unsaturated epoxy ester, which is a reaction product, is produced by adding a polybasic carboxylic acid anhydride to the hydroxyl group formed together with the ester group by ring opening of the epoxy group, or to the hydroxyl group originally formed in the epoxy resin itself. Forms a carboxylic ester.

This acid anhydride addition exhibits good adhesion, including having urethane bonds in the addition reaction product.

Examples of polybasic carboxylic anhydrides used include succinic anhydride, phthalic anhydride, trimellitic anhydride, hetacetic anhydride, tetrahydrophthalic anhydride, and maleic anhydride. It is used in a molar ratio of 0.05 or more to the hydroxyl group,
The acid value of the product is preferably about 5 to 100 during festival formation.

If the acid value becomes higher than this, the solvent resistance of the cured product will deteriorate.

The reaction between the epoxy resin component and carboxylic acids and the reaction between the generated epoxy ester and carboxylic anhydride are generally carried out using a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt such as triethylbenzylammonium chloride. It is carried out in the presence of a thermal polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether, and in the presence or absence of a solvent.

As the solvent, a photopolymerizable monomer that is one component of the photocurable composition can be used.

Examples of photopolymerizable monomers that also serve as solvents include vinyl acetate, vinyl propionate, and vinyl versatate (Shell Company product ■eOVa 10, vinyl ester of synthetic saturated carboxylic acid).

Vinyl compounds such as N-vinylpyrrolidone, 2-vinylpyridine, styrene, divinylbenzene, vinyltoluene, p-37th methylvinylbenzene, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid 2
- Acrylic esters such as ethylhexyl and benzyl acrylate and their corresponding methacrylic esters, ethylene glycol diacrylate, diethylene glycol diacrylate, nonaethylene glycol diacrylate, propylene glycol diacrylate, nonapropylene glycol diacrylate, isobutine glycol Polyfunctional acrylates such as diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate, and their corresponding methacrylates are used.

Of course, the photocurable composition can also be prepared by adding new or additional photopolymerizable monomers after forming the addition reaction product of the epoxy ester and the carboxylic anhydride; In addition to the photopolymerizable monomers mentioned above, reactive acrylates such as pentaerythritol triacrylate, 2-hydroxyethyl acrylate, and 2-hydroxypropyl acrylate, and methacrylates corresponding to these can also be used.

Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin phenyl ether, benzointhionityl ether, benzointhiophenyl ether, furoin, tesyl chloride, 2-methylanthraquinone, 2- Commonly used compounds such as ethyl anthraquinone, 2-bromoanthraquinone, 2-nitroanthraquinone, acetophenone, benzophenone, ω-chloroacetonephenone, p-chlorobenzophenone, Michler's ketone, thiomichler's ketone, and dithiocarbamates are photocurable. It is used in an amount of about 0.2 to 5% based on the weight of the composition.

The photocurable composition prepared from each of these components has a composition of about 1 to
Preferably, the viscosity is on the order of 500 poise (25°C), and adjustment to such a viscosity is achieved by adjusting the relative proportions of the photopolymerizable monomers, which proportions are generally determined by the composition. It is approximately 20 to 80% of the weight.

The photocurable composition is cured by light irradiation, generally by ultraviolet irradiation or electron beam irradiation, but the curing speed is different from that of epoxy ester using only an epoxy resin without internal urethane bonds as the epoxy resin component. There is no particular slowdown compared to the case where an addition reaction product with a polybasic carboxylic acid anhydride is used.

The cured product of the photocurable composition has excellent adhesion to various substrates, and the storage stability of the photocurable composition itself before irradiation with light is also good.

As mentioned above, an addition reaction product of an unsaturated epoxy ester and Yoshita basic carboxylic acid anhydride obtained by the reaction of a general epoxy resin that does not have a urethane bond in its molecule and a photopolymerizable basic carboxylic acid, By adding a partially amorphous saturated polyester to a photocurable composition containing a photopolymerizable monomer and a photopolymerization initiator, the adhesiveness of the cured product obtained therefrom is improved; Similarly, in the photocurable composition using an epoxy resin having a urethane bond in the molecule as the epoxy resin component according to the present invention, if a partially amorphous saturated polyester is added to the composition, The adhesion of the cured product to various substrates is further improved.

The saturated polyester added to the composition is saturated in its backbone and therefore non-reactive in its backbone and is partially amorphous.

Such saturated polyesters include polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, and butylene glycol, and acynic acid, azelaic acid, sebacic acid, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, etc. It can be obtained by reacting a saturated polycarboxylic acid or an acid anhydride thereof.

Crystalline saturated polyesters such as polyethylene terephthalate are modified with isophthalic acid, oxybenzoic acid, etc.
It can be used partially amorphous.

The saturated polyester is generally added in a proportion of about 1 to 20% based on the weight of the photocurable composition excluding the photopolymerization initiator, and if added in a proportion greater than that, separation of layers may occur.

The saturated polyester can be added to the photocurable composition by any method and at any desired time.

Generally, after the curable component (varnish) in the photocurable composition is prepared, it is added to this together with a photopolymerization initiator, but it is also possible to add it during the reaction for preparing the varnish. be.

The addition of such saturated polyesters further improves the adhesion of the cured product; in contrast, unsaturated polyesters do not exhibit good adhesion on their own, so such additions do not improve adhesion at all. I won't let you.

Furthermore, as mentioned above, the cured product of a photocurable composition containing a photocrosslinkable polymer having a photopolymerizable group in the main chain or side chain as a curable polymer component is inferior in terms of adhesiveness. ,
In the photocurable composition according to the present invention, even if such a photocrosslinkable polymer is used as a curable component and is mixed up to about 90%, preferably about 80% of its weight, the cured product Adhesion is well maintained.

This also means the modification of photocurable compositions containing photocrosslinkable polymers.

In this way, in the photocurable composition, the coexistence of the addition reaction product of the urethane bond-containing epoxy ester and the carboxylic acid anhydride adds a photopolymerizable group to the main chain or side chain that improves adhesion. Examples of photocrosslinkable polymers include glycols such as polypropylene glycol and diethylene glycol, dibasic unsaturated carboxylic acids such as maleic acid and fumaric acid, or their acid anhydrides such as maleic anhydride, and if necessary, isophthalic acid. A polymer having a photopolymerizable group in the main chain represented by an unsaturated polyester obtained by reacting a dibasic saturated carboxylic acid such as a dibasic saturated carboxylic acid or an acid anhydride thereof such as phthalic anhydride, and β-vinyloxyethyl acrylate, β-vinyloxyethyl meccrylate, β-vinyloxyethyl crotonate, β-
Homopolymers or copolymers such as vinyloxyethyl turbate, epoxy resins and α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and optionally maleic acid, adipic acid, and phthalic acid. unsaturated epoxy esters obtained by reacting acids, polybasic carboxylic acids such as tetrahydrophthalic acid, unsaturated epoxy esters obtained by reacting epoxy resins with hydroxyalkyl acrylates, hydroxyalkyl methacrylates, etc., and these unsaturated epoxy esters. Urethane compounds of esters, polybasic carboxylic acid anhydride addition reaction products, reaction products of this acid anhydride addition reaction product with N-methylolacrylamide, α,β-unsaturated carboxyls such as glycidyl acrylate, glycidyl methacrylate, etc. Ring-opening copolymers of glycidyl esters of acids and polybasic carboxylic acid anhydrides, addition reaction products of addition polymers of glycidyl esters of α,β-unsaturated carboxylic acids with α,β-unsaturated carboxylic acids , hydroxy, alkyl acrylate, hydroxyalkyl methacrylate, etc., and polyols and polyisocyanates. Examples include polymers having a photopolymerizable group in the side chain, such as addition reaction products of.

Next, the present invention will be explained with reference to examples.

Comparative example epoxy resin DER331-J (epoxy equivalent weight 190)
A mixture of 190 g of acrylic acid, 36 g (0.5 mol) of adipic acid, 36.6 g (0.25 mol) of adipic acid, 4 g of triethylbenzylammonium chloride as a catalyst and 0.4 g of hydroquinone as a thermal polymerization inhibitor was added to 90
After reacting at ~120°C for 2 hours, 14.8 g (0.1 mol) of phthalic anhydride was added thereto, and the reaction was continued for an additional 30 minutes.

After the reaction was completed, 80 g of nonaethylene glycol diacrylate and 160 g of styrene were added to the reaction mixture to prepare a varnish.

This varnish has a viscosity of 3.7 boids (at 25°C) and a
It has an acid value of 2.8.

Example 1 Epoxy resin DER331-J 85.5,? , urethanized epoxy resin EP'U-10 (epoxy equivalent: 32
0-360) 17 g, acrylic acid 18.9 (0.25 mol), adipic acid 18. :1 (0,125 mol), 2 g of triethylbenzylammonium chloride, 0.2 g of hydroquinone, and 40 g of nonaethylene glycol diacrylate were reacted at 80 to 130°C for 2 hours, and then 7.4 mol of phthalic anhydride was added to the mixture. g (0.05 mol) was added and the reaction was continued for an additional 30 minutes.

After the reaction was completed, 80 g of styrene was added to the reaction mixture to prepare a varnish.

This varnish has a viscosity of 10.7 poise (25°C) and an acid number of 12.3.

Example 2 DER331-J used in the reaction of Example 1
The reaction and varnish preparation were carried out in the same manner as in Example 1, except that 76 g of EPU-10 was used and 34 g of EPU-10 was used.

The varnish obtained has a viscosity of 10.7 poise (25° C.) and an acid number of 11.8.

Example 3 DER331-J used in the reaction of Example 1
The reaction and varnish preparation were carried out in the same manner as in Example 1, except that 57 g of EPU-10 was used and 68 g of EPU-10 was used.

The varnish obtained has a viscosity of 17.6 poise (25° C.) and an acid number of 11.3.

Example 4 DER331-J used in the reaction of Example 1
The reaction and varnish preparation were carried out in the same manner as in Example 1, except that 47.5 g of EPU-10 was used and 85 y of EPU-10 was used.

The resulting varnish has a viscosity of 18.0 poise (25° C.) and an acid number of 10.8.

Example 5 In the reaction of Example 1, EPU-15 (epoxy content 450 to 510) was used as the urethanized epoxy resin at 24
The reaction and varnish preparation were carried out in the same manner as in Example 1, except that G was used.

The resulting varnish has a viscosity of 12.2 poise (25° C.) and an acid number of 10.1.

Example 6 In the reaction of Example 4, the same reaction and preparation of a varnish were performed as in Example 4, except that 120 g of EPU-15 was used as the urethanized epoxy resin.

The varnish obtained has a viscosity of 18.6 poise (25°C) and an acid number of 9.3.

Example 7 The same reaction and varnish preparation as in Example 4 were carried out, except that the same amount of triethylene glycol diacrylate was used instead of nonaethylene glycol diacrylate.

The resulting varnish has a viscosity of 21.0 poise (25° C.) and an acid number of 12.1.

Example 8 In the preparation of the varnish of Example 4, instead of styrene, 1
00 g of 2-hydroxyethyl acrylate was used.

The varnish obtained has a viscosity of 25.3 poise (25° C.) and an acid number of 12.5.

Example 9 Urethane epoxy resin EPU-10170, 9° Acrylic acid 18.9 (0.25 mol), Adipic acid 18.3
g (0,125 mol), 2 g of triethylbenzylammonium chloride, 0.2 g of hydroquinone and 50 g of tetrapropylene glycol diacrylate were reacted at 80 to 120° C. for 2 hours, and this was mixed with succinic anhydride 59 (0,0, 5 mol) was added thereto, and the reaction was continued for an additional 30 minutes.

After the reaction is complete, add to the reaction mixture.

A varnish was prepared by adding 120 g of - and p-mixed chlorostyrene.

This varnish has a viscosity of 25.6 poise (25° C.) and an acid number of 9.7.

Peel strength test of cured product of photocurable composition 2% by weight of benzoin ethyl ether (
However, in Example 8, a photocurable composition was prepared by adding 2 wt. Apply one coat using a 3KW ultra-high pressure mercury lamp to 30Crf1. It was irradiated for 3 minutes from a distance of .

After the cured film was left to stand for 24 hours, the peel strength (18° C.) between the cured film and the copper plate was measured using an Instron type peel tester.

A tape peel test and elongation measurements were also conducted.

All of the prepared photocurable compositions were heated at 40°C under light shielding.
It exhibits storage stability for 60 days or more and does not gel during that time.

Table 1 Example f.

Open Peel strength Tape Note) (g/cIrL) Peel test comparison example 1 71 〃 7 380 ◎ 〃8 753 ◎ 〃9 730 ◎ Note) ◎: No change at all, ○: Almost no change, ×: Total peeling From the above results, it was found that epoxy resin with urethane bonds in the molecule was used as a curable component. It can be seen that the adhesive strength of the cured product of the photocurable composition prepared using the reaction raw material is significantly improved compared to the case where an epoxy resin having no urethane bond is used.

Example 10 To 100 parts by weight of the varnish prepared in Example 3, a predetermined amount of amorphous saturated polyester (Pylon #30 manufactured by Toyobo Co., Ltd.
0) to prepare a photocurable composition as described above,
The peel strength of the cured product was measured and a tape peel test was conducted.

Moreover, the storage stability of the prepared photocurable compositions was all 60 days or more.

Table 2 Poly viscosity ester (poise peeling frequency tape/I6 (parts by weight) 725°C) (g, 4) Peeling test 1 2
18.8 760 ◎2 4 21
．． 7 720 ◎3 6 34.6 74
0 ◎4 10 57.2 670
◎This result shows that the cured product of the photocurable composition containing the amorphous saturated polyester exhibits even better adhesion.

Example 11 Urethane epoxy resin EP' (J-10170g1 acrylic acid 18g (0.25 mol), adipic acid 18.
l (0,125 mol), 4 g of triethylbenzylammonium chloride, 0.49 g of hydroquinone and 100 g of nonaethylene glycol cyacrate,
After reacting at 80 to 130°C for 3 hours, 14.8 g (0.1 mol) of phthalic anhydride was added thereto, and the reaction was continued for an additional 30 minutes.

After the reaction was completed, 200 g of vinyltoluene was added to the reaction mixture to prepare a varnish.

This varnish has a viscosity of 138 poise (25°C) and a
It has an acid value of 1.3.

The varnish prepared in this Example 11 and the varnish prepared in the above-mentioned Comparative Example were mixed in various proportions, and photocurable compositions were prepared as described above based on this mixed varnish.

The elongation and peel strength of the cured product were measured,
A tape peel test was conducted.

Claims (1)

[Scope of Claims] 1. Reaction of an epoxy resin having a urethane bond in its molecule and a photopolymerizable basic carboxylic acid, or an epoxy resin having a urethane bond in its molecule, a photopolymerizable basic carboxylic acid, and a polybasic acid Adhesive and storage stable product containing an addition reaction product of an unsaturated epoxy ester obtained by the reaction between polybasic carboxylic acids and a polybasic carboxylic acid anhydride, a photopolymerizable monomer, and a photopolymerization initiator. A photocurable composition with excellent properties. 2. Reaction between an epoxy resin having a urethane bond in the molecule and a photopolymerizable basic carboxylic acid, or a reaction between an epoxy resin having a urethane bond in the molecule, a photopolymerizable basic carboxylic acid, and a polybasic carboxylic acid. A light containing an addition reaction product of an unsaturated epoxy ester obtained by the reaction and a polybasic carboxylic acid anhydride, a partially amorphous saturated polyester, a photopolymerizable monomer, and a photopolymerization initiator. Curable composition. 3. Reaction between an epoxy resin having a urethane bond in the molecule and a photopolymerizable basic carboxylic acid, or a reaction between an epoxy resin having a urethane bond in the molecule, a photopolymerizable basic carboxylic acid, and a polybasic carboxylic acid. Addition reaction product of unsaturated epoxy ester and polybasic carboxylic acid anhydride obtained by reaction, photocrosslinkable polymer having a photopolymerizable group in the main chain or side chain, photopolymerizable monomer, and photopolymerization A photocurable composition containing an initiator and having excellent adhesive properties and storage stability.