JPS5865717A - Actinic ray-curable composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to active energy curable composite soles, which can be cured in a very short time by irradiation with ultraviolet rays or electron beams, and which have excellent adhesion to base materials and bendability. Concerning active energy ray-curable compositions with excellent properties
Chill with things.

In recent years, active energy ray-curable compositions have been used in printing inks,
A wide range of applications are underway in the fields of Kuvya varnishes, coatings, adhesives, photoresists, etc., and representative examples include prepolymers, -, oligomers, etc. containing radically polymerizable double bonds such as acryloyl groups Nanatsuma
The main component is sensitizer 1 coloring agent that generates radicals when exposed to ultraviolet rays as needed, or bisphenol-type epoxy honeysuckle, alicyclic epoxy resin, polyglycidyl ester, etc. that generates radicals when exposed to ultraviolet rays. There are products that contain catalysts that generate Lewis catabolism.

Conventionally, when these active energy ray-curable coating compositions are used, the density 7W properties may be insufficient depending on the target metal material and the type of each machine coated board. However, there are problems with bending properties, punching properties, and other processing resistance.

It was not necessarily practical. Acrylic-modified epoxy resins that use acrylic-modified epoxy resin have a fast curing speed and high surface hardness. Products using acrylic-modified urethane resin have excellent flexibility but slow curing speed, and also have good adhesion to some non-absorbent substrates. However, there were problems such as the high viscosity of the mackerel resin.

The purpose of the present invention is to provide a tin plate that can be cured extremely quickly by irradiation with active energy rays, especially ultraviolet rays or electron beams.
Gold 1J4 materials such as TP8 plate, aluminum plate, alkyd resin, vinyl resin.

For painted boards coated with epoxy resin, phenolic resin, polyester resin-acrylic resin, etc.

Good adhesion? It is an object of the present invention to provide an i-chili resin composition which has excellent processing resistance such as bending property and punching property.

In other words, the present invention is based on the following general formula [! ], 40 to 600 parts by weight of a bifunctional oligomer (b) represented by the following general formula (n), 5 to 300 tft parts of an epoxy resin having an epoxy group, and all components. The present invention relates to an active energy-curable composite sole containing 0 to 10% by weight of a photosensitizer as a main component.

R=s fl Mushroom (however, in formula [I), R+ and R each independently represent a hydrogen atom or a methyl group, and inertia represents an integer from 1 to 5.
) 4 (However, in Formula 1 (n), ns and R- each independently represent a hydrogen atom or a methyl group, and p represents an integer of 2 to 6.

) In the present invention, the monomer (2) is a compound obtained by adding ethylene oxide or propylene oxide to phenol and esterifying it with acrylic acid or methacrylic acid. 3 is suitable, and the viscosity of this monomer is about 50 to 30 Q cps (25℃
) with clear liquid. When a compound having a Tsuru number of 6 or more is used, the cured film obtained is undesirable because it is soft and brittle.

If the amount of monomer used is less than the above-mentioned amount, problems will arise in the density and flexibility of the cured film, and the system will become highly viscous, making it difficult to work in the painting or printing process. On the other hand, if too much food is used, the cured film becomes weak and becomes impractical.

In the present invention, oligomer a) has phthalic anhydride and a hydroxyl group y! - Dihydroxyalkyl compound with?
After the reaction, unreacted substances were removed from the reaction system, and then (
A compound obtained by reacting meth)acrylic acid, and a dihydroxyalkyl compound having a hydrogen group at the end thereof, is represented by the general formula HO + CH mushroom + OH, and - p in the general formula is 2 Any compound that is an integer of ~6 may be used. If a dihydroxyalkyl compound with p of 7 or more is used, the obtained cured film will be weak and have low hardness, so it is not suitable.

The dihydroxyalkyl compound having a water moat group at the end used in this oligomer is as follows.

Examples include ethylene glycol, 1.3-7'robylene glycol, 1.4-butanediol, 1.5-bentanediol, and 1.6-hexanediol.
1.5-bentanediol or 16-hexanediol is used, and the general formula [a″3 is 1 to
The main component is a compound with an integer of 4, and the number average molecule is 70.
0~900. Viscosity (25℃) 400-700 cps
It is particularly preferable to use an oligomer C in the range of 20% to 30% by weight in terms of viscosity and workability when made into a paint.

In non-invention, oligomer 〇 is the above-mentioned 7-mer■1
40 to 600 for the 00 weight maximum! j: Front 5F!
, it is preferable that the compound be blended within the range.

If the blending amount □ is less than 40 overlapping parts, the resulting cured film will not be able to exhibit the excellent elongation t that is characteristic of oligoester diacrylate, and if the blending amount is 6.
If it exceeds 00 weight,! The hardness and adhesion of the chemical coating decrease, making it unsuitable.

The epoxy resin used in the present invention may have 1 or more epoxy groups, preferably 2 or more M, in 11 molecules; Aliphatic epoxide, alicyclic epoxy resin, etc. can be suitably used. Glycidyl ether type epoxy resins include bisphenol diglycidyl ether,
Bisphenol A di-β methyl glycidyl ether, bisphenol F diglycidyl ether, water-added bisphenol A f IJ cidyl ether, bisphenol alkylene oxide adduct diglycidyl ether,
There are novolac glycidyl ethers, polyalkylene/glycol diglycidyl ethers, epoxy urethane resins, etc. There are six types of glycidyl ester type epoxy resins such as phthal dispersion diglycidyl esters and dimer acid diglycidyl esters, and glycidylamine type epoxy resins include: Contains triglycidyl isocyanurate, etc.

Saitama linear aliphatic epoxy resins include epoxidized polybutadiene, epoxidized soybean oil, etc., and fatty cyclic epoxy resins include bis(3,4-epoxy-6-methylcyclohexylmethyl)azibe), 3. Examples include 4-epoxy-6-methylcyclohexylmethyl, 3,4-epoxy-6-methylcyclohexanecarboxylate, and the like.

This epoxy resin should be blended in an amount of 5 to 300 parts per 100 parts of the monomer (e).
is preferable, 5? If the mixture is less than t47 parts, metal materials such as tin plate, TFS plate, aluminum plate, etc.
and alkyd (R resin, vinyl resin, epoxy resin,
The adhesion to acrylic fingers and painted plates such as polyester resin is reduced, causing problems in bendability, punching resistance, and other processing resistance. If the amount exceeds 300 degrees, the hardness of the cured film will decrease and it will not be suitable for practical use.

In 1C of the present invention, when the actinic rays are ultraviolet rays,
Photosensitizer! One example of dust that needs to be added is hachenzoin,
Benzoin methyl ether.

Benzoin sensitizers such as benzoin ethyl ether, penzoin isopyl ether, benzoin isobutyl ether, α-chlorobenzoin, α-allylbenzoin, benzophenone-P-methylbenzophenone, P-
Chlorbenzophenone? Benzophenone sensitizers such as Hiller's ketone, quinone sensitizers such as anthraquinone and 2-methylanthraquinone, phenyl disulfide,
Sulfide sensitizers such as tetramethylthiclam monosulfide, thioxanthone sensitizers such as thioxanthone, 2-chlorothioxanthone, etc.! Used alone or in appropriate combinations. These photosensitizers are preferably used in an amount of 0 to 10% by weight based on the total composition.

In the present invention, it is used to improve the properties of the formed film or to lower the viscosity of the composition.

If necessary, a reactive monomer or an organic solvent can be blended as appropriate.For example, 2-hydroxyethyl (
meth)acrylate, 2-hydroxypropyl(meth)
Acrylate, trimethylolpropane 7-(meth)ac IJL'-)1 trimethylolpropane tri(meth)
Acrylate, pentaerythritol mono(meth)acrylate, pentaerythritol tri(meth)acrylate, styrene, vinyltoluene, N-vinylpyrrolidone, 3-phenoxy-2-hydroxypropyl(meth)
acrylate, chrycidyl (meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol mono(meth)acrylate, 1,4-butanediol di(meth)acrylate), 1,6-hexanethiol di(meth)acrylate.

Reactive monomers such as reaction products of bisphenol A and alkylene oxide and (meth)acrylic acid, or toluene and xylene.

Organic solvents such as ethyl cellosolve, hexalactone acetate, butyl cellosolve, and cyclohexanone can be blended.

Furthermore, in the present invention, if necessary.

Organic and inorganic pigments, two-body pigments, plasticizers, various resins,
Curing acceleration aid, antifoaming agent, high-grade fat@! Other stabilizing agents can be added.

The present invention will be described below with specific examples! explain. All parts in the examples indicate heavy carp parts.

Production Example 1 182 parts (1 mole) of 2 mole adduct of ethylene oxide of phenol, 72 parts (1 mole) of acrylic moat and p-)luenesulfone! ! 2 40 mmol, 20 mmol of Hyde-quinone monomethyl ether at 90-100℃ with stirring
The reaction was carried out for 10 hours, and the reaction was terminated when the rR value became constant. Place this product into a separatory funnel.

Added 500 parts of water and performed 7 washings - this washing 73
After repeating the process several times to remove unreacted substances,
(2) Monomer (a) was produced by carrying out fumigation in (f).

Examples 1 to 5 and Comparative Examples 1 to 3 The a paraboloids shown in Tables 1 and 2 were placed on a tin plate,
FS board, aluminum board, alkyd resin, vinyl resin, and acrylic resin coated boards were coated to a film thickness of 7μ, and exposed to 10P using a curtain beam-type condensing irradiation system.
．． (7 lines of RAD irradiation were performed to create a cured film R4 times.About this film.

Adhesion (fifth plate, peeling off cellophane adhesive tape).

Lead gi hardness. A 180° bending test was conducted and the results are shown in Table 3.

Table 1.

*1. Oil shell (2) = -> 0 people, bisphenol large epoxy resin 9 molecular weight approximately 900, epoxy equivalent approximately 4
50-500# Melting point 64-74°C.

*2, same as above, but 2 molecular weight approximately 1,400,
Epoxy equivalent 'about 900-1000, melting point 96-104
℃.

*3. Part name manufactured by Ube Industries, phthalic anhydride and 1.

One diacrylated product of the reaction product with 5-bentanediol has a molecular weight of 700 and a viscosity of 520 cpa (at 25 DEG C.).

Table 2.

*4. Bisphenol A type liquid epoxy resin manufactured by Yuka Shell Musume.

*5. Product name manufactured by Kyoeisha Yushi e-Kasa, phthalic anhydride.

Reaction product of ethylene glycol and methacrylic.

Examples 6 to 8 The same compositions as in Examples 1 to 3 were each added with 4 parts of benzoin ethyl ether and the compositions (referred to as Examples 6 to 8, respectively) were applied in the same manner as in Example 1. ,
Ozone-free hot water high pressure mercury pump (output 160 W/fi
)'%- was used, placed on a conveyor running at a speed of 5 minutes/minute, and subjected to ultraviolet door irradiation. A similar test bAw was conducted on this cured film, and the results are shown in Table 4.

patent applicant Toyo Ink Manufacturing Co., Ltd.

Claims (1)

[Claims] 1 Monofunctional monomer represented by the following general formula CI) ■1
7 parts by weight, 1 part by weight of 40 to 600 parts of the bifunctional oligomer represented by the following general formula (II). An active energy ray-curable composition containing as main components 5 to 300 parts by weight of an epoxy resin and 0 to 10 parts by weight of a photosensitizer based on all the components. (However, in formula 9 (, I), R1 and R 嘗 each independently represent one hydrogen molecule or a methyl group + full represents a number of 1 to 5 elephants.) 4 (However, # formula [■] Zhongkan Jun and R4 are Each independently a hydrogen atom or methyl m'4'9 represents an integer of 2 to 6. Fecalizable tissue collection.