JPH0459817A - Radiation curing resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin having excellent curing properties to radiation, excellent adhesivity to metal, etc., solvent resistance and boiling water resistance, comprising a specific copolyester polyol, a polyisocyanate compound and a specific compound. CONSTITUTION:The objective composition comprising (A) a copolyester polyol containing >=40mol% aromatic dicarboxylic acid as an acid component and >=20mol% 1,6-hexanediol as a glycol component, (B) a polyisocyanate compound and (C) a compound containing one or more (meth)acryloyloxy groups and one or more OH groups and optionally (D) a urethane acrylate resin having 1,000-20,000 molecular weight prepared by reacting a polyol and/or polyamine in an amount more than the component A and a (meth)acrylate compound having <500 molecular weight in the weight ratio of 80/20 to 20/80.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a radiation-curable resin composition that has excellent radiation curability, adhesion to metals and plastics, solvent resistance, boiling water resistance, and weather resistance. relating to things.

(Prior Art) Radiation-curable resins and resin compositions are used in various adhesives, coatings, inks, paints, and magnetic recording media because the curing process saves resources and energy, and high-performance films can be obtained. Development of applications such as binders is progressing. In particular, urethane acrylate resins are being studied in the various fields mentioned above because they have excellent properties such as radiation curability and toughness of the coating film after curing.

However, conventional urethane acrylate resins and resin compositions have insufficient adhesion to metals and plastics, and in particular no one showing satisfactory adhesion to polyethylene terephthalate has been obtained.

Furthermore, among the properties of the film after curing, it is currently not possible to obtain a film with sufficiently satisfactory performance in terms of solvent resistance, boiling water resistance, and weather resistance.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned conventional problems, and its purpose is to provide excellent radiation curability, adhesion to metals and plastics, solvent resistance, and An object of the present invention is to provide a radiation-curable resin composition having excellent boiling water resistance and weather resistance.

(Means for Solving the Problems) The present inventors have developed (1) a polyester polyol in which specific amounts of aromatic dicarboxylic acid are copolymerized as the acid component of the copolymerized polyester polyol, and specific amounts of 1,6-hexanediol are copolymerized as the glycol component. (2) introduce a compound having one or more (meth)acryloyloxy groups and one or more hydroxyl groups via the polyisocyanate compound, and if necessary, (4) introduce a compound other than (1) above. Urethane acrylate resin Pg having a molecular weight within a specific range obtained by reacting polyol and/or polyamine and extending the chain
When using a resin composition obtained by blending a specific amount of (meth)acrylate compound (B) with <^),
It has been found that a radiation-curable resin composition that has excellent radiation curability and overcomes the above-mentioned drawbacks can be obtained.

That is, the radiation-curable resin composition of the present invention has (1)
40 mol% or more of aromatic dicarboxylic acid as the acid component and 1,6% or more as the glycol component. 2 hexanediol
A copolymerized polyester polyol containing 0 mol% or more, (2) a polyisocyanate compound, (3) a compound having one or more (meth)acryloyloxy groups and one or more hydroxyl groups, and if necessary, (4) the above ( The molecular weight obtained by reacting with polyols and/or polyamines other than 1) is 1,000 to
20,000 urethane acrylate resin (A) and a (meth)acrylate compound (B) having a molecular weight of less than 500 in a weight ratio of 80/20 to 20/80. It is a composition.

The copolymerized polyester polyol (1) above consists of a dicarboxylic acid component and a glycol component.

The aromatic dicarboxylic acid which is an essential component in the present invention is a dicarboxylic acid having an aromatic group in the molecule, such as phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, etc. is cited as a representative example.

If necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid may be included.

Examples of copolymerizable dicarboxylic acids other than aromatic dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid;
Alicyclic dicarboxylic acids such as 1.2-hexahydrophthalic acid, 3-hexahydrophthalic acid, 1.4-hexahydrophthalic acid, perhydronaphthalene dicarboxylic acid, fumaric acid, maleic acid, itaconic acid, etc. Examples include unsaturated dicarboxylic acids, unsaturated alicyclic dicarboxylic acids such as tetrahydrophthalic acid and cyclobutene dicarboxylic acid, and oxyacids such as p-hydroxyethyloxybenzoic acid and ε-caprolactone.

As the glycol component, 1,6-hexanediol is essential. Examples of copolymerizable glycols other than 1,6-hexanediol include ethylene glycol, propylene glycol, 113-7"l:1 panediol, 1,4-butanediol, 1,5-bentanediol, neo Pentyl glycol, diethylene glycol, dipropylene glycol, 2,2.4 trimethyl to 1
．． 3-bentanediol, 1,4-cyclohexane dimetatool, spiroglycol, l,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, ethylene oxide adduct and propylene oxide adduct of bisphenol A, hydrogen Examples include ethylene oxide adducts and propylene oxide adducts of bisphenol A, and diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. If necessary, a small amount of triol and tetraol such as trinotylolethane, trimethylolpropane, glycerin, and pentaerythritol may be included.

In order to obtain a copolymerized polyester polyol from such a dicarboxylic acid component and a glycol component, synthesis may be performed using an excess amount of glycol raw material with respect to the dicarboxylic acid raw material. It is desirable to synthesize the copolymerized polyester so that the terminal carboxyl group is less than 50 eq,/10'g.If it is more than 50 eq,/10'g, it may cause problems in the reaction with the diisocyanate compound when synthesizing the urethane acrylate resin described below. If the number of active terminals becomes too large, the desired urethane resin cannot be obtained, and the radiation curability decreases.

The dicarboxylic acid component used in the present invention has an aromatic dicarboxylic acid content of 40 mol% or more, and the glycol component contains 1,6-hexanediol 20 mol% or more.

Outside this range, not only the adhesion to metals and plastics, especially polyethylene terephthalate, becomes poor, but also boiling water resistance, solvent resistance, and weather resistance are unfavorable.

(2) Polyisocyanate compounds used in the present invention include 2.4-) lylene diisocyanate, 2.6 tolylene diisocyanate, p-phenylene diisocyanate, biphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, Tetramethylene diisocyanate, 3.3'-dimethoxy-4,4'-biphenylene diisocyanate,
2,4-naphthalene diisocyanate), 3.3'-dimethyl-4,4'-biphenylene diisocyanate, 4.
4'-diphenylene diisocyanate, 4.4'-diisocyanate diphenyl ether, 1.5'-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1.3-diisocyanatemethylcyclohexane, 1.4-diisocyanatemethylcyclohexane , 4,4'-diisocyanate dicyclohexane, 4,4'-diisocyanate dicyclohexylmethane, isophorone diisocyanate and other diisocyanate compounds, or a dimer of 2,4-tolylene diisocyanate containing up to 7 mol% of the total isocyanate groups, hexa Examples include triisocyanate compounds such as a dimer of methylene diisocyanate.

Examples of compounds having one or more (meth)acryloyloxy groups and one or more hydroxyl groups include mono(meth)acrylates of glycols such as ethylene glycol, diethylene glycol, and hexamethylene glycol, 2-hydroxyethyl (meth)acrylates, Mono(meth)acrylates and di(meth)acrylates of triol compounds such as 3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane, glycerin, trimethylolethane, penta Examples include hydroxyl group-containing acrylic compounds such as mono(meth)acrylate, di(meth)acrylate, tri(meth)acrylate of polyols with 4 or more valences such as erythritol and dipentaerythritol, glycerin monoallyl ether, and glycerin diacryl ether. It will be done.

Examples of polyols and/or polyamines other than the above (]) include compounds listed as the glycol component of the copolyester polyol (1) above, such as ethylene glycol and propylene glycol, hexamethylene diamine, diaminodiphenylmethane, and N-methyljetanol. Examples include amines, high molecular weight polyamines having two or more primary or secondary amino groups in the molecule, such as terminally aminated polybutadiene, and water.

The radiation-curable resin of the present invention is produced by reacting the (1) copolymerized polyester polyol and (2) the polyisocyanate compound to obtain an isocyanate-terminated prepolymer, and then (3) one or more (meth)acryloyloxy base and 1
A compound having 1 or more hydrogen groups, and if necessary,
(4) It can be obtained by reacting polyols and/or polyamines other than those mentioned in (1) above.

Another manufacturing method is a method in which the compounds to be reacted are charged all at once and reacted.

In addition, if necessary, -NR2, -NRze, -3 at any stage of the method for obtaining polyurethane acrylate
03M, -COOM, -PO(OM')z, >PO(
OM') (In the formula, R represents a hydrogen atom, alkyl, aryl, or aralkyl group, M represents a hydrogen atom, an alkali metal atom, tetraalkylammonium, or tetraalkylphosphonium, and M' represents a hydrogen atom, an alkali metal atom, or a tetraalkyl phosphonium. By reacting compounds with polar groups such as alkylammonium, alkyl, aryl, and aralkyl groups, it is possible to improve adhesion to various substrates and uniform dispersion of pigments, additives, etc. can.

The molecular weight of the urethane acrylate resin (A) of the present invention thus obtained must be within the range of 1,000 to 20,000. If the molecular weight is less than 1,000, distortion during curing will occur. If it becomes too large, the adhesion to the substrate will deteriorate, which is undesirable. If it exceeds 20,000, the compatibility with the (meth)acrylate compound (B) described below will become poor, and the viscosity will become too high, making it difficult to use. This is undesirable due to problems such as:

As another essential component of the present invention, the molecular weight is less than 500 (
Examples of the meth)acrylate compound (B) include methyl (meth)acrylate, ethyl (meth)acrylate, (
Butyl meth)acrylate, 2-ethylhexyl(meth)
Acrylate, 2-hydroxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, phenoxyethyl (meth)acrylate, tolyloxyethyl (meth)acrylate, benzyl (meth)acrylate, butoxyethyl (meth)acrylate, dicyclo Pentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycidyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, isobornyl (meth)acrylate, ethylene oxide modified phosphoric acid (meth)acrylate, N- Monoacrylate compounds such as methylvinylpyrrolidone, caprolactone-modified tetrahydrofurfuryl (meth)acrylate, (meth)acryloxyethyl succinate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, ethylene glycol di(meth)acrylate,
1.6-hexanethiol di(meth)acrylate, neopentyl glycol di(meth)acrylate, diethylene glycol (meth)acrylate, tripropylene glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate,
Dicyclopentenyl di(meth)acrylate, bisphenol A di(meth)acrylate, ethylene oxide modified phosphoric acid di(meth)acrylate, ethylene oxide modified bispheno-7L/A di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. diacrylate compounds, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)
Acrylate, triacrylate compounds such as propylene oxide-modified trimethylolpropane triacrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic acid-modified dipentaerythritol tetra(
Examples include tetraacrylate compounds such as meth)acrylate.

Since these (meth)acrylates (8) have excellent adhesive properties to polyethylene terephthalate, the following general formula (
This is a (meth)acrylate compound represented by 1).

A-(CHz), lB... (1) Among these, particularly preferred compounds are tetrahydrofurfree-
acrylate, phenoxyethyl acrylate, tolyloxyethyl acrylate, and benzyl acrylate.

Radiation-curable resin compositions using these compounds are
Radiation curability, adhesion to metals and plastics, especially polyethylene terephthalate, boiling water resistance,
It is preferred because it has excellent solvent resistance and weather resistance.

The radiation-curable resin composition of the present invention comprises the above-mentioned urethane acrylate resin (A) and (meth)acrylate compound (B).
), and the blending ratio is (by weight)
A)/(B) = ranges from 80/20 to 20/80. If (^) is less than 20% by weight, the properties as a urethane acrylate resin will be lost, and the adhesion to metals and plastics, solvent resistance, and weather resistance will decrease, which is undesirable. is 80% by weight
If it exceeds 100%, the viscosity will be too high, making it difficult to use, and the curing property against radiation will be poor, which is undesirable.

As a method for producing the radiation-curable resin composition of the present invention, there is a method in which the urethane acrylate resin (A) is synthesized by the method described above, and then the (meth)acrylate compound (B) is blended. Another method is to synthesize the urethane acrylate resin (A) using the (meth)acrylate compound (B) as a reaction solvent.

An organic solvent can be added to the radiation-curable resin composition of the present invention. Organic solvents are limited to volatile ones, and most or all of them must be volatilized by a heating drying ring before radiation curing. Usable solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran, dioxane, and ethylene glycol monoethyl ether, benzene, toluene, and xylene. aromatic R-hydrogens such as hexane, aliphatic hydrocarbons such as heptane, methanol,
The solvent used in the synthesis of the urethane acrylate resin (A) of the present invention, such as alcohols such as ethanol and isopropyl alcohol, or mixtures thereof, can also be used as is.

Radiation used in the present invention includes ultraviolet rays, electron beams, T-rays, neutron beams, and the like. When using ultraviolet radiation, it is desirable to add a photoinitiator to the radiation-curable coating composition.

Photoinitiators include acetophenone, benzophenone,
benzoin ethyl ether, benzyl methyl ketal,
Benzyl ethyl ketal, hendiine isobutyl ketone, hydroxydimethyl phenyl ketone, 1-hydroxycyclohexylphenyl ketone, 2,2-jethoxyacetophenone, Michler's ketone, 2-hydroxy-2-
Methylpropiophenone, benzyl, diethylthioxanthone, 2-chlorothioxanthone, hendiylethoxyphosphine oxide, 1-1-limethylbenzoyldiphenylphosphine oxide, and the like can be used. Also, if necessary, photosensitizers such as n-butylamine, dibutylamine triethylamine, etc. may be used.

The scanning method or curtain beam method can be used as the electron beam irradiator, and the absorbed dose is 1 to 20 Mra.
d Preferably 2 to 15 Mrad, absorbed dose I
If the curing reaction is less than 20 Mrad, the curing reaction is insufficient.
If it exceeds d, the energy efficiency used for curing may decrease or excessive crosslinking may proceed, which is not preferable.

The radiation curable resin composition of the present invention has excellent radiation curability, adhesion to metals and plastics,
Taking advantage of its excellent solvent resistance, boiling water resistance, and weather resistance, it can be used in a variety of applications such as adhesives, coating agents, inks, paints, resist materials, and binders for magnetic recording media.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

In the examples, parts simply indicate parts by weight.

<Production example of copolymerized polyester polyol> In a reaction vessel equipped with a thermometer, stirrer, distillate, condenser, and pressure reducing device, 440 parts of dimethyl terephthalate, 440 parts of dimethyl isophthalate, 279 parts of ethylene glycol, 274 parts of hexanediol, and 0.5 part of tetrabutoxytitanate were charged and heated at 150 to 230°C for 120 minutes to cause transesterification.The reaction system was then depressurized to 1018g and heated to 250°C for 30 minutes to carry out the reaction. A copolymerized polyester-polyol A was obtained.

The molecular weight of polyester polyol A was 2.000. Polyester polyols B-E obtained by a similar method are shown in Table 1. The resin composition was analyzed by HNMR.

Table 1 After dissolving, add 22 parts of isophorone diisocyanate and 0.05 part of dibutyltin dilaurate, and
After reacting for 2 hours, 12 parts of 2-hydroxyethyl acrylate was further added and the reaction was carried out at 70 to 80°C for 5 hours to obtain radiation-curable resin composition A, which is a phenoxyethyl acrylate solution of urethane acrylate resin. The molecular weight of the urethane acrylate resin was 3,000. A urethane acrylate resin was synthesized by the same method to obtain a radiation-curable resin composition BG. The resulting compositions are shown in Table 2.

Examples of producing radiation-curable resin compositions are shown below in the margins> 100 parts of copolyester polyol A and 134 parts of phenoxyethyl acrylate were charged into a reaction vessel equipped with a thermometer, a stirrer, and a reflux type condenser. Comparative Example 1 Radiation-curable resin compositions A to G shown in Table 2 were placed on a polyethylene terephthalate sheet with a thickness of 10I after curing.
It was applied using an applicator so that the amount of paint was 110%.

Next, electron beam irradiation was performed at an accelerating voltage of 165 KV, a current of 2.5 m^, and an absorbed dose of 7.5 Mrad to form a cured film. Cured films were produced on galvanized steel sheets, polycarbonate sheets, polyimide sheets, and vinyl chloride sheets using the same method.

The cured film was evaluated using the following method.

The 0 gel fraction cured film was placed in a thimble filter paper and extracted with methyl ethyl ketone for 24 hours using a Soxhlet extractor. After drying the residue in the 0 cylindrical source paper, it was weighed and the insoluble content was determined from the weight before extraction. The weight fraction of was calculated and used as the gel fraction.

Adhesion was tested by cutting 1 x 100 base lines on the film with a cutter, pasting cellophane tape on it, and peeling it off.

○The surface of the dissection-resistant cured film was coated with gauze soaked in ethanol for 50 minutes.
The surface condition after rubbing twice was observed.

O: No abnormality.

Δ: There are scratches.

×: The coating film peels off.

○ Boiling Water Resistance After immersing the cured film in spring water, it was boiled for 2 hours and the surface condition of the film was visually judged.

○: No abnormality.

Δ: Slightly cloudy or slightly peeled.

×: Severe clouding or peeling.

Changes in gloss after 300 hours of exposure were visually determined using an accelerated weathering tester (QUV).

O: No abnormality.

Δ: Gloss slightly decreases.

×: Gloss is severely reduced.

Comparative Example 2 In Example 1, instead of radiation-curable resin compositions A to G, phenoxyethyl acrylate, which is a component of radiation-curable resin composition A, was replaced with methyl ethyl ketone, and 80% was used before electron beam irradiation. A cured film was prepared and evaluated in the same manner as in Example 1, except that it was dried by heating at .degree. C. for 20 minutes.

Comparative Example 3 An attempt was made to produce a cured film in the same manner as in Example 1 except that phenoxyethyl acrylate was used instead of radiation-curable resin compositions A to E in Example 1, but it did not cure by electron beam irradiation. , it was not possible to conduct an evaluation.

Below are margins Example 2 and Comparative Example 4 2.5 parts of 2-hydroxy-2-methylpropiophenone was added to 100 parts of the radiation-curable resin composition A-E shown in Table 2, and a polyethylene terephthalate sheet was prepared. A cured film was prepared by applying ultraviolet rays at 500+J/cj using a 6.4 KWX J light water-cooled low-pressure mercury lamp. Galvanized steel sheet by the same method,
A cured film was prepared on a polycarbonate sheet, a polyimide sheet, and a vinyl chloride sheet, and evaluated in the same manner as in Example 1.

Comparative Example 5 In place of radiation-curable resin compositions A to E in Example 2, phenoxyethyl acrylate, a component of radiation-curable resin composition A, was replaced with methyl ethyl ketone, and the temperature was heated to 80°C before ultraviolet irradiation. Evaluation was conducted in the same manner as in Example 2, except that the sample was dried by heating for 20 minutes.

Comparative Example 6 An attempt was made to produce a cured film in the same manner as in Example 2 except that phenoxyethyl acrylate was used instead of radiation-curable resin compositions A to E, but the film did not harden due to ultraviolet irradiation. It was not possible to conduct an evaluation.

The following margin (effects of the invention) The radiation-curable resin composition of the present invention has excellent radiation curability, and the film after hardening and curing has excellent adhesion to metals and plastics, solvent resistance, spring water resistance, and weather resistance. You can obtain products with excellent properties.

hand Continued Supplementary Positive book (spontaneous) November 21, 1990 Patent applicant: Toyobo Co., Ltd. 1゜ & Display of incidents 1990 Patent Application No. 173887 name of invention Radiation curable resin composition person who makes corrections Relationship to the case Patent applicant 2-2-8 Dojimahama, Kita-ku, Osaka & “Detailed description of the invention” column in the specification Contents of correction Correct "hydrogen" to "hydroxy acid".

■Page 14, line 3 Insert "compound" after "(meth)acrylate".

■　Page 14, line 4 After "excellent points", insert "preferred compounds".

) Line 14 of Table 2 on page 21 of the same of In Table 3 on page 25 of the same Correct.

correct.

-1 to

Claims (4)

[Claims] (1) A copolymerized polyester polyol containing 40 mol% or more of aromatic dicarboxylic acid as an acid component and 20 mol% or more of 1,6-hexanediol as a glycol component, (2) polyisocyanate compound, (3) A compound having one or more (meth)acryloyloxy groups and one or more hydroxyl groups, and if necessary, (4) The molecular weight obtained by reacting with a polyol and/or polyamine other than (1) above is 1,000 to 20,
000 urethane acrylate resin (A) and molecular weight 5
The (meth)acrylate compound (B) less than 00 is 80
1. A radiation-curable resin composition comprising: a weight ratio of /20 to 20/80.