JPS6254711A - Urethane-modified acrylate resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition lowly irritating to the skin, excellent in workability, applicability, adhesion, waterproofness, weathering resistance, etc., and suitable for paints, etc., by mixing a specified urethane-modified acrylate with 1,9-nonanediol diacrylate. CONSTITUTION:The purpose urethane-modified acrylate resin composition (A) is obtained by mixing a urethane-modified acrylate of the formula (wherein R1 and R1' are each H or methyl, R2 and R2' are each a polyalcohol residue, R3 is an organic diisocyanate residue, R4 is a bivalent organic group, m is 1-5 and l and n are each 1-3) with 1,9-nonanediol diacrylate (B). Component A is produced from a polyester polyol obtained from an organic dibasic acid and a low-MW polyalcohol, an organic diisocyanate (e.g., tolylene diisocyanate) and a hydroxyl group-containing (meth)acrylate (e.g., 2-hydroxyethyl acrylate).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a composition comprising a urethane-modified acrylate and a specific reactive diluent, which is cured to produce a highly durable urethane-modified acrylate resin. Many resin compositions that can be cured by radiation have been developed.
It has begun to be used in paints, adhesives, pressure-sensitive adhesives, binders for magnetic tapes, etc., and its range of use is expected to further expand in the future. Among them, urethane-modified acrylates are weakly anaerobic and can polymerize even in high oxygen concentrations, and the physical properties of the cured product depend on its structure (type of diisocyanate,
They vary greatly depending on the type of polyol, molecular weight, degree of condensation, etc.), and are attracting attention because of their great variety. As urethane-modified acrylate resins consisting of urethane-modified acrylate and polymerizable monomers, those having various compositions are known (for example, Japanese Patent Publication No. 15629/1982, Japanese Patent Application Laid-open No. 1983-1989).
13693, JP 48-25095, JP 5F1-54316, JP 59-1917
72 newsletter, etc.).

Since the urethane-modified acrylate that the invention aims to solve has a urethane skeleton, a cured product with toughness can be obtained. However, due to the cohesive force of urethane bonds and relatively high molecular weight, it is a viscous liquid or solid at room temperature, which poses problems in terms of production and use. Therefore, when used as a paint or adhesive, it is essential to reduce the viscosity, and various reactive diluents are used in combination. The performance required for this diluent is that it does not adversely affect paint properties and N-contact customization, has excellent compatibility with urethane-modified acrylates and other additives, has low skin irritation, and has good hardening properties (hardening properties). M is superior in speed, volumetric shrinkage, elastic modulus of cured film, flexibility, adhesion, adhesion, durability, strength and elongation).
It is essential. In particular, the compatibility between these reactive diluents and the urethane-modified acrylate has an important meaning and greatly influences the physical properties of the cured film.

Therefore, it is necessary to pay particular attention to the selection of the structures of the reactive diluent and the urethane-modified acrylate.

From this point of view, conventional 1,6-hexanediol diacrylate has a large dilution effect, has excellent weather resistance, hydrolysis resistance, and flexibility of the cured film, and has a fast curing speed. It is highly irritating ((PII value 5.5), and its use is quite limited.More recently, soft
t>*, there are an extremely large number of applications that require readability,
In addition, the hydrolysis resistance, weather resistance, etc. of the cured film are strictly required, and improvement thereof is desired.

The purpose of the present invention is to provide a urethane-modified acrylate resin composition that causes less skin irritation, has a low viscosity, and has excellent workability and usability.Another purpose of the present invention is to provide a urethane-modified acrylate resin composition that causes less skin irritation, has a low viscosity, and has excellent workability and usability. Another object of the present invention is to provide a composition that produces a urethane-modified acrylate resin that is excellent in strength and elongation, flexibility, elasticity, Wi-adhesiveness, and adhesiveness.

According to the present invention, the above-mentioned object is achieved by the general formula (1) (wherein R1 and RS are hydrogen or a methyl group, RzO? re Ro
! + Kumanamawani, -- Mitsugu, Peng Feng, p-densocyanate residue, R4 is a divalent organic group, m is a number from 1 to 5, L and n are integers from 1 to 3 1 as a reactive diluent for turethane-modified acrylate represented by ○)
．． This was achieved by using 9-nonanediol diacrylate.

The urethane-modified acrylate used in the present invention is manufactured from polyester polyol, organic diisocyanate, and hydroxyl group-containing acrylate or methacrylate, has a urethane bond in the polymer main chain, and has an acryloyl group or methacryloyl group at the polymer end. A polymer represented by the above general formula (1).

The polyester polyol has an average molecular weight of 11,200
~10,000 polyester polyols are preferred, but
This polyester polyol is composed of a conventional organic dibasic acid and a low molecular weight polyhydric alcohol. As the organic dibasic acid, adipic acid, succinic acid, sepathic acid, azelaic acid, terephthalic acid, inphthalic acid, maleic acid, etc. can be used.

In addition, low-molecular polyhydric alcohol is 1,4-butanediol%
1,6-hexane glycol, 1,9-nonanedi
Luol, diethylene glycol, propylene glycol
low coal, trimethylolpropane, glycerin,
3-methyl-1,5-bentanediol, etc. are used. ε-caprolactone and β-methyl-δ-
Polyester polyols obtained by ring-opening polymerization such as batarellolactone can also be used.Among these, particularly preferred polyester polyols include those containing at least one group selected from the following formula as a constituent component of the polyester polyol. By using a polyester polyol containing the constituent component, a composition with even better hydrolysis resistance, weather resistance, and flexibility can be provided.
Polymerization 0 0 0
0 Oh 1
, lt-C-0-(C1(2), -0
-C-, -0C-(CH2)7C-0-telepolyester polyol specifically refers to 3-methyl 1.5-
Synthesized from bentanediol or a molecular polyol containing it and a dicarboxylic acid such as adipic acid, cono-phosphoric acid, tarlic acid, pimelic acid, cepacic acid, azerai, terephthalic acid, isophthalic acid, maleic acid, and dicarboxylic acid. It is a polytyl polyol.

Ester polyols having -OCHz CHCHCHCH2CO- groups in their molecules are specifically polyol mixtures containing poly(β-thyl-δ-valerolactone) polyols, or polyol mixtures containing poly(β-methyl-δ-valerolactone) polyols, or It is a block or run copolymer polyol obtained by ring-opening as one component.

(β-methyl-δ-valerolactone)phorylha, β-
It is obtained by ring-opening polymerization of methyl-δ-valerolactone with a low-molecular polyol such as di-glycol or butanediol.

In addition, copolymers with other lactones, such as those obtained by ring-opening copolymerization of ε-caprolactone and β-methyl-δ-valerolactone, can be obtained by copolymerizing ε-caprolactone and β-methyl-δ-valerolactone randomly or in blocks within their molecules. BoFs
It is also possible to use a polyol in which the CO- group is modified, or a Glock polymer polyol consisting of an adipate polyester polyol and β-methyl-δ-valerolactone. Chilled polyvarnishes with 6 carbon atoms and mail branches have overall excellent hydrolysis resistance, solvent resistance, and flexibility, and at the same time have particularly good pigment dispersibility.In general, odd-numbered carbons are straight lines. It appears that polyesters arranged in a straight line are better in terms of pigment dispersibility than those with even numbers.Furthermore, because they have methyl branches, they have good low-temperature flexibility. Excellent adhesion to the base material.
C (CH2),! O-M t-.

ll1 It is derived from 1,9-nonanediol or azelaic acid. By using these glue esters with a carbon number of 9, low-temperature properties, flexibility, softness, and resistance to foaming agents,
A composition with excellent overall hydrolysis resistance, etc. and excellent pigment dispersibility can be obtained.

The organic diisocyanate used in the present invention may be any known aromatic, aliphatic, or alicyclic isocyanate having two incyanate groups. For example, 4,4-diphenylmethane diisocyanate, P-phenyl diisocyanate, toylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate,
xamethylene diisocyanate, inphorone diisocyanate), 4,4-dicyclohexylmethane iso7anate, bis(incyanatomethyl)chlorohexane, and the like.

Examples of acrylates or methacrylates containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 1,9-nonanediol mono(meth)acrylate,
Examples include propylene oxide-modified mono(meth)acrylate, caprolactone-modified mono(meth)acrylate, trimethylolethane di(meth)acrylate, trimenalol propane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and the like.

When curing by UV, when comparing acryloyl groups and methacryloyl groups, the reaction rate of acryloyl groups is overwhelmingly fast, and it is preferable to use acrylates.

The reaction ratio between the polyester polyol and the organic diisocyanate is based on the hydroxyl group (
OH) is less than 1 (
0) 1/NCO<1). By reacting at the above reaction rate, a prepolymer containing terminal isocyanate groups can be obtained. The reaction temperature is 20-130°C, especially 5O-
Preferably, the temperature is 100°C. Suitable catalysts include triethylenediamine, triethylenetin, digtyltin dilaurate, dimethyloctyltin, and the like.

Terminal isocyaner IJ submerged by the above reaction! The containing prepolymer is then reacted with a hydroxyl group-containing (meth)acrylate to produce a urethane-modified acrylate. When water is added to the group-containing (meth)acrylate, the compound (reaction bone ratio OH
/NC0) is preferably equal to or more than the equivalent mole. The molecular weight of this urethane-modified acrylate is 1000~
20000. More preferably 2000-1500
It is 0.

The urethane-modified acrylate-l- obtained by the above reaction is then mixed with 1,9-nonanediol diacrylate, which is an anti-hexavalent diluent, to prepare a urethane-flexible acrylate resin composition. Urethane modified acid.

The mixing ratio of rylate and 1.9-nonanediol diacrylate is 95:5 to 5:95, preferably 90:10 to 3.
0 Near 0 (weight ratio).

The 1,9-nonanediol diacrylate used in the present invention has a PII value of 2.0, υ, and 1.6.
-PlI value of hexanediol diacrylate of 5.5
It is extremely low compared to , which is advantageous in terms of handling. Furthermore, 1,9-nonanediol diacrylate is comparable to 1,6-hexanediol diacrylate and 1,3-neopentyl glycol diacrylate in terms of dilution ability, curing speed, and volumetric shrinkage. Further, the compatibility with the urethane-modified acrylate is very good, and it is possible to provide a urethane-modified acrylate resin that has a large viscosity-lowering effect and excellent workability.

In order to further improve the adhesion and adhesion performance of the composition obtained in this way to gold g4 etc., the general formula (II
) (In the formula, R5 is hydrogen or a methyl group, R6 is a divalent organic group, q is 1 or 2, r is 1 or 2, and q-)-r
= 3) A phosphorus-containing (meth)acrylate represented by: Phosphorus-containing (meth)acrylates include mono[2-(meth)acrylate ethyl] phosphate, mono[2-(meth)acrylate propyl], di[2-(meth)acrylate], and di[2-(meth)acrylate].
-(meth)acrylate ethyl], di[2-(meth)acrylate propyl phosphate], and the like.

The addition of phosphorus-containing (meth)acrylate is 50% of the total resin.
It is preferably less than % by weight. Furthermore, there is no problem in using other polyfunctional acrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate, and monofunctional acrylates such as dicyclopentadienyl acrylate, 2-etherhexyl acrylate, and benzoyloxyethyl acrylate.

Further, in order to prevent radical polymerization of the produced urethane-acrylate, about 0.001 to 0.05% by weight of a radical polymerization inhibitor can be added to the system.

Examples of the inhibitor include hydroquinone, hydroquinone monomethyl ether, and the like.

Examples of means for curing the composition of the present invention include: When curing the composition of the present invention by ultraviolet light curing, ultraviolet curing, thermosetting, or any other known means thereof, a photoinitiator such as the one shown below may be used. Added. That X-(book m)
Examples include benzophenone, p-methoxypenzophenone, acetophninone, flobiophenone, xa7ton, benzoin, benzoin ethyl ether, anthraquinone, naphthoquinone, etc., and the amount thereof is approximately 0% relative to the urethane-modified acrylate contained in the composition. .1～
Add approximately 15% by weight. In addition, methylamine,
- Photoactive agents such as dimeethanolamine, N-&tilgetanolamine, tributylamine may be added.

When curing the composition of the invention by heat.

Known radical polymerization initiators - such as hydrogen peroxide, benzoyl peroxide, cumene peroxide, t-
Butyl hydroperoxide, azobisbutyronitrile, etc. can be used. When curing by electron beam irradiation, it is not particularly necessary to add a photoinitiator or radical polymerization initiator.

No matter which of these curing methods is adopted, the urethane-modified acrylate resin obtained by the present invention is tough and has excellent hydrolysis resistance, weather resistance,
Provides a cured product with scorbability, adhesion, and adhesive properties. In addition, the internal strain caused by volumetric shrinkage during curing is small, making it particularly useful as an adhesive.0 The composition of the present invention may be filled with any filler other than the above-mentioned compounding agents as long as it does not impair the purpose of the present invention. Agents and additives may also be added depending on the purpose of convenience.

More specifically, the urethane-modified acrylate bait obtained by the present invention is useful in paints, coatings, adhesives, ink sealants, and the like.

Examples In order to explain the present invention more specifically, the following examples are given below.
A comparative example will be given. In the example, "center part" indicates parts by weight.

The performance of the cured coating film was determined by the following method.

(a) Dense ia: How many out of 100 test pieces were adhered to x/
Shown as 100.

(11) Flexibility: A tanzak-shaped test piece of 5 g and length 10 I:IL was bent along the outer periphery of a cylinder with a diameter of 2 cIL, and the test piece was evaluated based on whether or not the coating cracked.

(iii) Water resistance: Place the test piece in pure water at 40°C for 24 hours.
After immersion for 0 hours, the appearance and adhesion of the outer coating layer (method according to (1) above) were evaluated.

Qv) Weather resistance; Sunshine weather off the test piece.
The sample was kept in a thermostat for 600 hours, and the appearance and adhesion of the outer coating layer (method according to (i) above) were evaluated.

Example 1 920.0 parts m of 3-methyl-1,5-bentanediol
Adipine@876f (diol/acid molar ratio 1.3/
1) Esterification was carried out under normal pressure while passing N2 gas and distilling condensed water at a temperature of about 210°C. When the acid value of the polyester became 0.3 or less, the degree of vacuum was gradually increased using a vacuum pump to complete the reaction. In this way, a purple polyester polyol (hereinafter referred to as polyester (11)) having a hydroxyl value of 56 and an acid value of 0.1 was obtained. This polyester (JL) is liquid at room temperature and has a molecular weight of approximately 2. There was ooo”c.

To 500 parts of this polyester (a) were added 111 parts of inphorone diisocyanate and 0.2 parts of di-n-butyltin silacrate as a catalyst, and the mixture was heated and stirred at 80°C for 6 hours to form a urethane prepolymer A containing terminal incyanato groups. I got it.

Next, 58 parts of 2-hydroxyethyl acrylate and 0.4 part of hydroquinone monomethyl ether were added, and the mixture was reacted at 60°C for 6 hours. urethane-modified acrylate resin composition [! ] was obtained.

Obtained urethane-modified acrylate resin composition [1]
100 parts IIC hengeine ethyl ether 3 parts t- were added to make a coating composition v4. Apply this on an aluminum ξ dilam board with a 75 micron applicator and output 9 Q
Irradiation was performed with a high-pressure mercury lamp of W/cttt. The violet is 6
By irradiating it 2 times at a speed of m/min, it became hardened to 7 degrees, and by irradiating it 4 times, it was cured to pure gold.

A coating film irradiated six times was used to determine the -j properties.

Examples 2 to 7 Urethane-modified acrylate resin compositions with the compositions shown in Table 1 were obtained in the same manner as in Example 1.

Comparative Examples 1 to 3 In the same manner as in Example 1, urethane-modified acrylate resin compositions having the compositions shown in Table 1 were obtained.

The physical properties of the coating film of the cured product of each resin composition, the tensile strength of the film, and the elongation at break were measured and are listed in Table 1.

In addition, the blending ratios of adipic acid and isophthalic acid, azediic acid and isophthalic acid, and 3-methyl-1,5-pentanediol and 1,9-nonanediol in Table 1 are all 1/1.
(molar ratio). In addition, the blending ratio of urethane-modified acrylate, reactive diluent, and initiator is the same as in implementation fA31. Effects of the invention

Claims (1)

[Claims] (1) Urethane-modified acrylate resin composition consisting of urethane-modified acrylate and 1,9-nonanediol diacrylate represented by general formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) thing. [In the formula, R_1 and R_1' are hydrogen or a methyl group, R
_2 and R_2' are polyhydric alcohol residues, R_3 is an organic diisocyanate residue, R_4 is a divalent organic group, m is a number from 1 to 5, and l and n are integers from 1 to 3. ] (2) R_ in urethane-modified acrylate (I)
4 is selected from ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The urethane-modified acrylate resin composition according to claim 1, characterized in that it contains at least one group as a constituent component. (8) The urethane according to claim 1 or 2, characterized in that the third component is an acrylate represented by the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) Modified acrylate resin composition. [In the formula, R_5 is hydrogen or a methyl group, R_6 is a divalent organic group, q is 1 or 2, r is 1 or 2, and q+r=3. ]