JPS5932484B2 - Photocurable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that can be photocured by irradiation with light such as ultraviolet rays, and is particularly suitable for coating metal or synthetic resin surfaces or forming electrical insulating films. Regarding the composition.

Photocurable resins or resin compositions containing acrylates such as epoxy acrylate, epoxy methacrylate, polyester acrylate, and urethane acrylate or unsaturated polyester as a main component are known as photocurable resins or resin compositions.

However, the above-mentioned acrylate-based photocurable resins generally have poor adhesion to metals, and unsaturated polyesters have poor heat resistance, so their practical applications are currently limited. be.

Therefore, the present invention provides a photocurable resin composition that has superior electrical properties, heat resistance, adhesion, etc., and can be used in a wide range of fields compared to conventionally known photocurable resins or resin compositions. This is what we are trying to provide.

That is, the present invention provides the following advantages: ＾ a) Maleic anhydride and water are added to the addition polymer of cyclopentadiene and 1|3-pentadiene at 140°C.
A monovalent unsaturated carboxylic acid obtained by the reaction below,
(B) A polymer obtained by reacting an acidic carboxylic acid having at least one acryloyl group or methacryloyl group at the end of the molecule and also having a carboxyl group in the molecule with f→epoxide, (B) α, A monomer having a β-unsaturated double bond in the molecule and a photosensitizer (C) are essential components, and the weight ratio of the components (2) and (2) is (A)/(2)= This is a photocurable resin composition characterized in that it is contained in a ratio of 90/10 to 30/70.

In the present invention, f() used in the production of the (to) component
Monovalent unsaturated carboxylic acids are cyclopentadiene and 1,
A first step, which is an addition polymerization reaction with 3-pentadiene;
It is obtained through a second step, which is an addition reaction of the reaction product with maleic anhydride and water.

Note that such an addition polymer is, for example, QN-0301 (
It is commercially available from Nippon Zeon Co., Ltd. under the trade name RX-0330-WAX).

<Second Step> In the second step, the ratio of the addition polymerization product and maleic anhydride is preferably approximately equimolar, and the amount of water is preferably selected to be slightly in excess of the maleic anhydride.

On the other hand, if the reaction temperature in the second step exceeds 140°C, one of the reaction components (addition polymerization product) will partially distill out of the reaction system, making it difficult to obtain the desired monovalent unsaturated carboxylic acid. temperature must be 140°C or less. (b) Acid carboxylic acid (2) used in the production of six components in the present invention
Ester) is a compound having at least one acryloyl group or methacryloyl group at the end of the molecule and a carboxyl group in the molecule, for example, the general formula [wherein R1 is hydrogen or a methyl group and R2 is It is a residue of a polyhydric alcohol compound, R3 is a residue of an aromatic or alicyclic polycarboxylic acid, m is a number from 1 to 3, and n is a number from 1 to 3.

] Examples include aromatic or alicyclic carboxylic acids represented by the following. These acidic carboxylic acid ethers may be obtained by any known method, but for example, per mol of organic polycarboxylic acids, especially aromatic or alicyclic polycarboxylic acids, hydroxyl Obtained by selecting 2 moles or more, preferably about 2.5 to 6 moles, of an acrylate compound or methacrylate compound having an alkyl group at the end and carrying out an esterification reaction in the presence of an esterification catalyst such as an organic quaternary ammonium salt. Any product having at least one carpoxyl group may be used.

Here, the organic polycarboxylic acids constituting one component of one of the reactions have at least two or more carboxyl groups, especially two or more carboxyl groups.
Aromatic or alicyclic polycarboxylic acids having ~5 carboxyl groups are preferred. Further, this aromatic or alicyclic polyhydric carboxylic acid may be a so-called acid anhydride having an intramolecular acid anhydride group that can be a carboxyl group. Examples of such polycarboxylic acids include phthalic anhydride, trimellitic anhydride, phthalic anhydride derivatives such as pyromellitic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3/,4,4/benzophenonetetracarboxylic dianhydride, bis(3,4-
dicarboxyphenyl)ether dianhydride, bis(3,
Examples include chiaromatic polycarboxylic acids having two benzene rings such as 4-dicarboxyphenyl) methanodianhydride, alicyclic polycarboxylic acids such as methyl nadzic anhydride, nadzic anhydride, and tetrahydrophthalic anhydride. .

Acrylates or methacrylates having a hydroxyalkyl group in the molecule, which constitutes another reaction component to obtain the acidic carboxylic acid (ester) mentioned above, are produced by an esterification reaction between a polyhydric alcohol such as a diol compound and acrylic acid. It has at least one hydroxyalkyl group and an acryloyl or methacryloyl group.

However, such compounds include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monoacrylate. Examples include methacrylate, pentaerythritol triacrylate, glycerin diacrylate, and glycerin monoatrylate. In addition, in the esterification reaction to obtain the acidic carboxylic acid (ester) in (b), for the purpose of preventing gelation, a known suitable thermal polymerization agent such as hydroquinone, 2,6-ditertiarybutyl-para-cresol, or parabenzoquinone is used. It is preferable to add a small amount of a stabilizer to the reaction solution.

Moreover, the polymerizable monomer described below can be used as a solvent for the esterification reaction. The polymer (4) used in the present invention includes (6) a monovalent unsaturated carboxylic acid containing a maleic acid double bond, (2) an acid carboxylic acid ester containing an acryloyl group or a methacryloyl group, and (2) an acid carboxylic acid ester containing an acryloyl group or a methacryloyl group;
It is obtained by addition-reacting the epoxide of (3) in the presence of an addition catalyst and, if necessary, in the coexistence of a polymerization inhibitor.Canoloponic acid and epoxide have an equivalent ratio of carpoxyl groups to epoxy groups of 1 or approximately 1. It is preferable that the

The reaction is carried out at, for example, 80 to 120°C. The epoxide (c) above is a compound containing one or more, preferably two or more, epoxy groups per molecule, such as a polyhydric alcohol or a polyhydric alcohol. Glytudyl polyethers of monovalent phenols, epoxidized fatty acids or drying oil acids, epoxidized diolefins, esters of epoxidized diunsaturated acids, etc. are used, and oligomers of these are also used. However, the above-mentioned catalysts include metal halides such as zinc chloride and lithium chloride, sulfides such as dimethyl sulfide and methyl phenyl sulfide,
Sulfoxides such as dimethyl sulfoxide and methyl sulfoxide, tertiary amines such as N,N-dimethylaniline, pyridine, triethylamine, benzyldimethylamine and their salts or bromates, tetramethylammonium chloride, trimethyldodecylbenzylammonium chloride, etc. Quaternary ammonium salts, sulfonic acids such as para-toluenesulfonic acid, and mercaptans such as ethyl mercaptan and propyl mercaptan are used.

On the other hand, examples of polymerization inhibitors include hydroquinone, tertiary-butylcatechol, P-benzoquinone, and 2,5-ditertiarybutylhydroquinone.

In the present invention, monomers having α,β unsaturated double bonds, which are component (b), include styrene, α-methylstyrene, chlorostyrene, vinyltoluene, vinylnaphthalene, esters of acrylic acid or methacrylic acid, acetic acid or propionic acid. vinyl esters, maleic acid, fumaric acid and itaconic acid esters alone or in combination.
Used in combination of more than one species.

In particular, in the present invention, the weight ratio (A)/(B) of component (4) and component (8) is limited to 90/10 to 30/70.

The reason for this is that if it exceeds 90/10, the viscosity of the composition will be high and workability will be significantly impaired;
This is because if it is less than that, the toughness of the film cannot be obtained, and it is generally preferable to mix (A)/8 in a weight ratio of 80/20 to 40/60. Furthermore, in the present invention, other curable resins such as oligoester acrylates, epoxy esters, polybredienes, unsaturated polyesters, etc. may be blended into the combined system of components (A) and (0) within a range that does not impair the properties. In the present invention, photosensitizers that serve as a polymerization initiator, which is component (C), include benzoin, benzoin alkyl ethers such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, benzointhioethers, and benzophenone. , acetophenone, 2-ethylanthraquinone, decyl chloride, etc. However, the amount used is based on the total polymerizable component [(A)
, 03) and other curable resins added as necessary], 0.5 to 10% by weight? degree, preferably 1
~5 weight 70. That is, if the weight is less than 0.5 70,
This is because the curing speed becomes slow, and if the amount exceeds 10% by weight, film forming properties tend to be lost.

The resin composition according to the present invention may be composed of only three components, the above-mentioned component (4), component 8, and component (O);
A so-called radical polymerization initiator such as a hydroperoxide such as tert-butyl peroxide, a ketone peroxide such as methyl ethyl ketone, or an oxy peroxide such as dicumyl peroxide is used in an amount of 0.5 to 5.
weight? (preferably 1 to 3% by weight) may be used in combination.

Of course, in this case, 0.01 to 1 (preferably 0.05 to 0.4) of a known curing accelerator such as a metal naphthenate is added by weight. Additional amounts may be added. Furthermore, the resin composition according to the present invention is
For example, aluminum hydroxide, calcium carbonate, silica,
Fillers and reinforcing agents such as alumina, glass fibers, and organic fibers may be added and blended as appropriate.

Next, examples of the present invention will be described.

Examples 1 to 3 First, a monovalent unsaturated carboxylic acid and an acidic carboxylic acid (ester) constituting one reaction component of component (4) were manufactured as follows.

(a) Production of monovalent unsaturated carboxylic acid Maleic anhydride 9809, water 2
509, FfQN-0330-WAXl (trade name, Nippon Zeon Co., Ltd.) which is an addition polymer of cyclopentadiene and 1,3-pentadiene 27509, and hydroquinone 0
．． 29 was charged and reacted at 140°C for 3 hours under a nitrogen stream, dehydration was performed under reduced pressure, and an absorption peak due to the acid anhydride ring (1770 CrrL) was determined by infrared absorption spectrum analysis.
-1,1850c! A semi-solid monovalent unsaturated carboxylic acid 38809 having an acid value of 128 without n-1) was obtained.

(b) A capacitor for producing acidic carboxylic acid (ester);
In a four-bottle flask equipped with a nitrogen inlet tube, a thermometer, and a stirrer, 1429 g of phthalic anhydride, 120 g of 2-hydroxyethyl acrylate, 0.029 g of hydroquinone, and 0.4 g of triethylbenzylammonium chloride were added.
9 was charged and the esterification reaction was carried out at 95°C for 5 hours under a nitrogen stream.

Next, unreacted acrylate was distilled off under reduced pressure to obtain acidic phthalic acid monoacrylate (PA-HEA) 2 which had no absorption peaks (1770cf11-1, 1850crf1-1) due to acid anhydride rings by infrared absorption spectroscopy.
I got 609.

This PA-HEA has an acid value of 210 and a viscosity of 160 boads (3
0°C). In addition, in the above reaction, the reaction was carried out under the same conditions except that trimellitic anhydride 1929 was used instead of phthalic anhydride, and the acid value was 350 and the viscosity was 220 Boaz (
Approximately 3049 of acidic trimellitic acid monoacrylate ester (TMA-HEA) having a temperature of 30°C was obtained.

Further, in the above reaction, the reaction was carried out under the same conditions except that tetrahydrophthalic anhydride 1329 was used as the acid anhydride, and 2-hydroxyethyl methacrylate 1209 was used as the acrylate compound, and the acid value was 206 and the viscosity was 1.
70 boads (30'C) acidic tetrahydrophthalic acid monoacrylate ester (THPA-HEA) approx. 265
I got a 9.

Monovalent unsaturated carboxylic acid (USC) and acidic carboxylic acid monoacrylate ester (PA-HEA, TMA-HEA, THPA-HEA) respectively synthesized as above
, fl Epicote 828W1 (trade name, Ciel Kagaku Co., Ltd.) as an epoxide and trienalbenzylammonium chloride were selected in the composition ratios (parts by weight) shown in Table 1, and charged into a four-necked flask equipped with a condenser, etc., and filled with nitrogen. After carrying out the esterification reaction at 95°C for 8 hours under air flow (the acid value of the reaction system was 10),
Predetermined amounts of sunalene and benzoylethyl ether were added and mixed to prepare three types of photocurable resin compositions.

On the other hand, unsaturated polyester-based (Comparative Example 1) and epoxy methacrylate-based (Comparative Example 2) photocurable resins were prepared for comparison.

Each of these resins was coated on a tin plate, a copper plate, and a Funinol laminate (0.5 x 70 x 100 mm) using a bar coater #28.
A cured film having a thickness of 35 to 40 μm was formed by applying light using a 2Kw high-pressure mercury lamp as a light source at an irradiation distance of 100 μm.

The results of measuring the appearance, hardness, adhesion, etc. of these cured films are also shown in Table 1. In Table 1, adhesion was measured by applying adhesive cellophane tape to the cured film and peeling off the tape, and heat resistance was measured by taking 6g of a sample into a 60mmφ tin plate and cracking the cured film. The insulation resistance was measured according to JISC21O5, and ◯ indicates good quality and × indicates poor quality.

As is clear from the above specific examples, all of the compositions according to the present invention can be easily cured by light irradiation.

Furthermore, the cured resin exhibits excellent adhesion to metals and also has excellent heat resistance and electrical insulation properties.

Claims (1)

[Claims] 1 (A) (a) Maleic anhydride and water are added to the addition polymer of cyclopentadiene and 1,3-pentadiene to
A monovalent unsaturated carboxylic acid obtained by reacting at 40°C or lower; (b) an acidic carboxylic acid having at least one acryloyl group or methacryloyl group at the end of the molecule and a carboxyl group in the molecule; ) A polymer obtained by reacting with an epoxide, (B) a monomer having an α,β unsaturated double bond in the molecule, and (C) a photosensitizer as essential components, and the above (A) component and A photocurable resin composition containing component (B) in a weight ratio of (A)/(B) = 90/10 to 30/70. 2 The ratio of component (A) to component (B) is 80/20 to 40
2. The photocurable resin composition according to claim 1, wherein the photocurable resin composition has a hardness of /60. 3. The photocurable resin composition according to claim 1 or 2, wherein the component (B) is styrene.