JPH09316157A - Photocurable resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition excellent in the adhesion to polyolefin reins and its use. SOLUTION: This composition is prepared by mixing a sensitizer and desirably a reactive diluent with a urethane (meth)acrylate resin obtained by allowing a polyester resin prepared by polycondensing an acid component comprising a polybasic acid with a glycol component comprising a branched diol having 2 C or higher alkyls as side chains and hydrogenated polybutadienepolyol to enter into an addition reaction with a diisocyanate compound and reacting the product with a urethane (meth)acrylate resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable resin composition which can be cured by irradiation with active energy rays such as ultraviolet rays. More specifically, it has excellent adhesiveness (adhesion) to polyolefin. The present invention also relates to a photocurable resin composition comprising a polyester resin having excellent transparency and its use.

[0002]

2. Description of the Related Art Generally, polyester resins have heat resistance,
Although it is excellent in weather resistance and the like, it is used in various applications, and is particularly effectively used in the fields of molded articles, adhesives, pressure-sensitive adhesives, and paints. JP-A-59-21537
No. 3, as a hot melt adhesive, a short-chain ester unit composed of an organic dicarboxylic acid containing an aromatic dicarboxylic acid as a main component and an alkylene glycol, an organic dicarboxylic acid containing an aromatic dicarboxylic acid as a main component, and 1,2 A long-chain ester unit composed of polybutadiene glycol or a hydrogenated product thereof and / or a 1,2-polybutadiene dicarboxylic acid or a hydrogenated product thereof and a long-chain ester unit composed of an alkylene glycol has been proposed.
Further, JP-A-3-167284 proposes an aliphatic polyester using a dicarboxylic acid or polyol having a hydrogenated polybutadiene structure as an adhesive.

[0003]

However, the pressure-sensitive adhesive disclosed in JP-A-3-167284 is a solvent-type pressure-sensitive adhesive that requires the addition of a solvent, and in recent years, the use of a solvent has been considered in view of environmental problems and the like. It is regarded as a problem, and there is a demand for an alternative to a solvent system that is cured by active energy rays such as ultraviolet rays. In addition, the above-mentioned JP-A-59-2153.
In the resin compositions described in JP-A No. 73 and JP-A-3-167284, no consideration is given to the adhesiveness (adhesion) to the polyolefin resin. Polyolefin-based resins have excellent chemical properties and are excellent in properties such as being lightweight and inexpensive, so they have been widely used in molded products.However, polyolefin-based resins such as polyethylene and polypropylene are non-polar and crystalline. Because of its high adhesiveness, the adhesiveness with various adhesives is extremely poor, and the adhesiveness with the formed coating film is poor even when various paints are applied. This point makes polyolefin resin applicable to various applications. This has become a major difficulty in the process, and development of a resin having excellent adhesion (adhesion) performance to a polyolefin resin is desired.

As a countermeasure against this problem, Japanese Patent Laid-Open No. 61-7370 discloses an aromatic dicarboxylic acid or its derivative, a dimer acid or its hydrogenated product or a derivative thereof, and an aliphatic dicarboxylic acid or its derivative other than dimer acid as an acid component. And a thermoplastic copolymerized polyester elastomer containing a alkylene glycol having 2 to 10 carbon atoms and a long-chain glycol having an average molecular weight of 350 to 6000 and having no ether bond in the molecule as a glycol component, and the thermoplastic copolymerized polyester elastomer. Although an adhesive composition consisting of a low-molecular weight thermoplastic material having a volatile property has been proposed, as a result of a detailed study by the present inventors, the above composition is not yet satisfactory, and the high degree of recent technology Further improvement is required in accordance with the trend. Therefore, under such a background, the present invention does not require a solvent that solves the above problems, and a photocurable resin composition comprising a polyester resin having excellent adhesiveness (adhesiveness) to a polyolefin resin and the use thereof. The purpose is to provide.

[0005]

[Means for Solving the Problem] However, as a result of intensive studies to solve the problem, the present inventors have found that polybasic acid (A) is an acid component and an alkyl group having 2 or more carbon atoms Polyester resin (I) obtained by polycondensing a branched diol (b-1) having a chain and a hydrogenated polybutadiene polyol (b-2) as a glycol component (B), and at least carbon as a polybasic acid (A). Aliphatic dicarboxylic acid (a-1) having a number of 2 to 20, or at least a carbon number of 2
It is preferable that the aliphatic dicarboxylic acid (a-1) and the aromatic dicarboxylic acid (a-2) of 20 are contained, and the side chain has an alkyl group having at least 2 carbon atoms as a polybasic acid (A) component. After adding the diisocyanate compound (C) to the polyester resin (I) obtained by polycondensation containing the branched polybasic acid (a-3), the hydroxyl group-containing (meth) acrylate (D) is reacted, A resin (II) obtained by the reaction (hereinafter referred to as a urethane (meth) acrylate-based resin (II)) with a sensitizer (III), preferably a reactive diluent (IV). The present invention has been completed by finding out that a curable resin composition meets the above-mentioned object and further finding out that such a resin composition is excellent in transparency and curability.

That is, according to the present invention, the glycol component (B) has a branched diol (b) having an alkyl group having 2 or more carbon atoms in its side chain.
-1) and the hydrogenated polybutadiene polyol (b-2) are the greatest feature, whereby the photocurable resin composition comprising the polyester resin of the present invention has an adhesive property (adhesiveness) to a polyolefin resin. ) Is excellent
Further, it also has excellent transparency and curability.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The polyester resin (I) of the present invention comprises a polybasic acid (A) as an acid component and a branched diol (b-1) having a side chain of an alkyl group having 2 or more carbon atoms and a hydrogenated polybutadiene polyol (b-2). And a glycol component (B) containing as an essential component. The polybasic acid (A) used in the present invention is not particularly limited as long as it is a divalent or higher acid, but among them, at least an aliphatic dicarboxylic acid having 2 to 20 carbon atoms (a-1), Or at least 2 to 20 carbon atoms
It is preferable to include the aliphatic dicarboxylic acid (a-1) and the aromatic dicarboxylic acid (a-2).

Aliphatic dicarboxylic acid having 2 to 20 carbon atoms (a
As -1), for example, succinic acid, glutaric acid, 2,2
-Dimethylglutaric acid, pimelic acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid and the like, among which dodecanedicarboxylic acid, sebacic acid and azelaic acid are particularly preferred in terms of compatibility. Examples of the aromatic dicarboxylic acid (a-2) include terephthalic acid, isophthalic acid, phthalic anhydride, phthalic acid, 1,4
-Naphthalic acid, 1,5-naphthalic acid, diphenic acid, 4,4'-oxybenzoic acid, diglycolic acid, 4,
Examples thereof include 4'-sulfonyldibenzoic acid and 2,5-naphthalenedicarboxylic acid. Of these, terephthalic acid and isophthalic acid are particularly preferred in terms of low cost and reactivity. However, it is not limited to these.

The compounding ratio of the aliphatic dicarboxylic acid (a-1) having 2 to 20 carbon atoms and the aromatic dicarboxylic acid (a-2) is (a-1) :( a-2) = 10: 90
˜100: 0 (weight ratio), preferably 20:80 to 7
It is desired to be 0:30. When the aromatic dicarboxylic acid (a-2) exceeds 90, the compatibility becomes poor, which is not preferable.

In addition to the above-mentioned polybasic acid component, in the present invention, it is also preferable to contain a branched polybasic acid (a-3) having an alkyl group having 2 or more carbon atoms, preferably 2 to 20 in the side chain. . Examples of the branched polybasic acid (a-3) include hydrogenated products of dimer acid and 1-butylhexanedicarboxylic acid. When a branched polybasic acid (a-3) is used,
It is desired that the blending amount thereof be 10 to 90% by weight, preferably 10 to 70% by weight, based on the whole acid component. If the blending amount is less than 10% by weight, the compatibility becomes poor and 90
When the content is more than 10% by weight, the cohesive force is weak and the adhesive force is lowered, so that the effect of the present invention is not remarkably exhibited.

The branched diol (b-1) having an alkyl group having 2 or more carbon atoms, preferably 2 to 20 carbon atoms as a side chain, which is an essential component of the glycol component (B), is 2,2'-butylethylpropanediol. , 2-ethyl-1,3-hexanediol and 2-methyl-2-n-propanediol, and one or more of them may be used. 2,2'-Butylethylpropanediol is preferably used. A hydrogenated polybutadiene polyol (b-2) is also used as an essential component of the glycol component (B). The hydrogenated polybutadiene polyol (b-2) has a structure represented by the following chemical formula 1, and has a molecular weight of 30:
It is preferably from 0 to 6000, particularly preferably from 500 to 3000.
The iodine value is preferably 0 to 50, preferably 0 to 20, and the hydroxyl value is preferably 15 to 400, preferably 30 to 250.

[0012]

Embedded image Here, n is an integer of 3 to 110.

In the present invention, an alkylene glycol having 2 to 20 carbon atoms is used as the other glycol component in addition to the glycol component (B) of the above (b-1) and (b-2). For example, ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol,
Trimethylene glycol, triethylene glycol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Examples thereof include 1,9-nonanediol and the like, and one or more kinds are used. Among them, ethylene glycol, 1,4-
Butanediol and the like are preferably employed.

The blending amount of each of the above glycol components is not particularly limited, but a branched diol having an alkyl group having 2 or more carbon atoms in its side chain (b-1): hydrogenated polybutadiene polyol (b-2): other Glycol component of
It is preferably 10 to 90:10 to 90: 0 to 80 (weight ratio). More preferably, a branched diol having an alkyl group having 2 or more carbon atoms in its side chain (b-1): hydrogenated polybutadiene polyol (b-2): other glycol component = 10 to 70:30 to 90: 0 to 60 ( Weight ratio). When the amount of the branched diol (b-1) having an alkyl group having 2 or more carbon atoms in its side chain is less than 10% by weight, the compatibility becomes poor, and when it exceeds 90% by weight, the adhesive strength is lowered, which is not preferable. On the other hand, if the hydrogenated polybutadiene polyol (b-2) is less than 10% by weight, the adhesion to the olefin will be poor, and if it exceeds 90% by weight, the cohesive strength of the resin will be weak, and as a result, the adhesion will be reduced. If the content of other glycol components exceeds 80% by weight, poor compatibility and a decrease in adhesive strength are not preferred.

Thus, in the present invention, the polyester resin (I) is obtained by polycondensing the above-mentioned acid component and glycol component, but the production method of the polyester resin (I) is not particularly limited, and it is known. It can be performed according to a usual method. For example, a method is employed in which the acid component and the glycol component are directly or simultaneously directly or stepwise esterified, or are subjected to a transesterification reaction followed by polycondensation. At that time, any of various catalysts, stabilizers, modifiers,
Alternatively, an additive or the like may be used. For example, examples of the esterification catalyst include dibutyltin oxide and zinc acetate, and examples of the polymerization catalyst include tetra-n-butyl titanate and antimony trioxide. Further, the acid component and the glycol component are in a molar ratio of acid component: glycol component = 1: 1.
It is desirable to carry out 1 to 1: 2.0, preferably 1: 1.2 to 1: 1.8.

Polyester resin (I) by the above method
The obtained polyester resin (I) is excellent in compatibility, and the polyester resin (I) has a molecular weight of 3,000 to 15,000, preferably 3,000 to
At 10,000, the viscosity is 1-3000 poise (120
℃), preferably 1 to 1500 poise (120 ℃), glass transition temperature (Tg) -60 to 50 ℃, preferably-.
The temperature is preferably 40 to 30 ° C., and the effect of the present invention is remarkably exhibited.

In the present invention, a diisocyanate compound (C) is then added to the polyester resin (I) and then a hydroxyl group-containing (meth) acrylate (D) is reacted to give a urethane (meth) acrylate resin. (II) is obtained. The diisocyanate compound (C) is not particularly limited, and may be any compound having two isocyanate groups in the molecule, for example,
Examples thereof include tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylol propane tolylene diisocyanate adduct, trimethylol propane xylylene diisocyanate adduct, isophorone diisocyanate, and diphenylmethane diisocyanate. Of these, tolylene diisocyanate and isophorone diisocyanate are preferably used.

As a method of adding the diisocyanate compound (C) to the polyester resin (I), 0.1 to 3 mol of the diisocyanate (C) is preferably added to 1 mol of the polyester resin (I), preferably 0.1. Add 5 to 2 mol, under normal pressure, 50 to 150 ° C, preferably 70 to 1
It is carried out by stirring at 20 ° C. for 1 to 20 hours, preferably 3 to 10 hours.

Examples of the hydroxyl group-containing (meth) acrylate (D) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Among them, 2-hydroxyethyl (meth) acrylate is preferable.

The hydroxyl group-containing (meth) acrylate (D)
Regarding the reaction method of, 0.1 to 3 mol, preferably 1 to 3 mol, preferably 1 mol of a resin (hereinafter referred to as polyester urethane resin) obtained by adding the diisocyanate compound (C) to the polyester resin (I) 0.5 to 2 mol is blended, 50 to 150 ° C, preferably 70 to 120 ° C
For 1 to 20 hours, preferably 3 to 10 hours, whereby a urethane (meth) acrylate resin (II) is obtained. The urethane (meth) acrylate resin (II) has a molecular weight of 4,000 to 20,000, preferably 4,000 to 15,000 and a viscosity of 1 to 5,000 poise (120 ° C.), preferably 1 to 3,000 poise (1).
20 ° C), glass transition temperature (Tg) -60 to 50 ° C,
It is preferably -40 to 30 ° C.

In the preparation of the urethane (meth) acrylate resin (II), after polycondensation and addition of the diisocyanate compound (C), the hydroxyl group-containing (meth) acrylate (D) is subsequently added to carry out the reaction. Alternatively, the resin once obtained at each stage is taken out, and then each reaction is performed on the resin. By mixing the urethane (meth) acrylate resin (II) thus obtained with the sensitizer (III), the photocurable resin composition of the present invention can be obtained, and the adhesiveness (adhesion) to the polyolefin is excellent. Further, the resin composition has excellent transparency and curability.

Specific examples of the sensitizer (III) include:
2-Hydroxy-2-methylphenylpropanone benzophenone, isopropyl benzoin ether and the like can be mentioned, but 2-hydroxy-2-methylphenylpropanone is particularly preferable. Regarding the blending amount of the sensitizer (III), the urethane (meth) acrylate resin (II) 100
0.1-20 parts by weight, preferably 1-1
It is desired to be 5 parts by weight. When the amount of the sensitizer (III) exceeds 20 parts by weight in such a blending amount, the adhesion (adhesion) is deteriorated, and when it is less than 0.1 parts by weight, curing is unsatisfactory, which is not preferable.

In the present invention, it is also preferable to add a reactive diluent (IV) in addition to the sensitizer (III), and the excellent adhesiveness of the present invention is exhibited. Specific examples of the reactive diluent (IV) include 1,4-butanediol diacrylate and 1,6-hexanediol diacrylate, with 2,2'butylethylpropanediol diacrylate being particularly preferred. To be Regarding the compounding amount of the reactive diluent (IV), the urethane (meth) acrylate resin (II) and the reactive diluent (IV) are mixed in the mixing ratio of the urethane (meth) acrylate resin (II): reactive diluent. (IV) = 95: 5 to 5:95 (weight ratio), preferably 90:10 to 30:70, more preferably 90: 1.
It is desired to be 0 to 40:60. If the reactive diluent (IV) exceeds 95% by weight in such a blending ratio, the adhesion becomes poor, and if it is less than 5% by weight, curing is unsatisfactory, which is not preferable.

Furthermore, 3 of urethane (meth) acrylate resin (II), sensitizer (III) and reactive diluent (IV) are used.
In the case of blending the components, the blending method is not particularly limited, and may be selected as appropriate, such as batch charging of three components or a method of blending the remaining one component after blending any two components.
If necessary, the urethane (meth) acrylate resin (II) is used in a solvent such as ethyl acetate, toluene, or methyl ethyl ketone to a concentration of 20 to 80% by weight, preferably 20 to 60%.
The sensitizer (III), preferably a reactive diluent (IV), is mixed with the urethane (meth) acrylate resin (II) and the sensitizer (III), preferably further reacted. It is also possible to add a functional diluent (IV) and adjust the concentration and viscosity with the above solvent.

The photocurable resin composition comprising the polyester resin of the present invention includes various acid derivatives such as dioctyl phthalate, diphenyl phthalate, triphenyl phosphate, glycol derivatives, glycerin derivatives, epoxy derivatives, low Medium molecular weight polyester-based plasticizers, polyether-based plasticizers, paraffin-based / naphthene-based / aromatic-based process oils, softeners such as castor oil, plasticizers or stabilizers, inorganic / organic fillers, pigments, etc. If necessary, the thermoplastic resin and the like can be contained in an amount that does not impair the effects of the present invention.

Thus, the photocurable resin composition of the present invention is
Not only metal and synthetic resin (except polyolefin),
Resins that have excellent adhesion (adhesion) performance to polyolefin resins such as polyethylene and polypropylene, which are non-polar and have high crystallinity and are extremely difficult to adhere to, and their molded products (films, sheets, cups, etc.) Since it is a composition and has excellent transparency and curability, it can be effectively used for applications such as paints, adhesives and coatings, especially for paints and adhesives.

It is effective that the photocurable resin composition of the present invention is applied as a paint to a substrate such as wood, metal, synthetic resin, leather or fiber and used for improving the surface of the substrate. In particular, in the present invention, when a molded article composed of a polyolefin resin among synthetic resins is used as a base material, the effects of the present invention are remarkably exhibited. In use, it is dissolved in a solvent such as ethyl acetate, toluene, methyl ethyl ketone, cyclohexanone, and isophorone, if necessary, and applied with a solution having a concentration of 10 to 60% by weight, or heated to a molten state for use. It is preferable. After coating, irradiation with active energy rays is performed from above the coating surface to cure. As the active energy rays, α rays, β rays (electron rays), γ rays, X
Although rays and ultraviolet rays can be used, β rays (electron rays) and ultraviolet rays are preferable from the viewpoint of industrial use. When using ultraviolet rays, it is preferable to irradiate with a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp or the like.

When the photocurable resin composition of the present invention is used as an adhesive, it may be dissolved in a solvent such as ethyl acetate, toluene, methyl ethyl ketone, etc. to prepare a solution or heated, as described above. Then, it can be made into a molten state or can be applied by a general applicator, a roll coater, a bar coater or the like. After application, the active surface is irradiated with active energy rays and cured as above. Further, the resin composition of the present invention is in the form of powder, chips,
It can be used after being formed into various forms such as tape, string, film or non-woven fabric.

[0029]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, “parts” and “%” are based on weight unless otherwise specified. Example 1 As the acid component, 0.2 mol of dodecanedicarboxylic acid, 0.8 mol of isophthalic acid (dodecanedicarboxylic acid: isophthalic acid = 28: 72 (weight ratio)), and as the glycol component, 2,2′-butylethylpropane 0.9 mol of diol, hydrogenated polybutadiene polyol (molecular weight 2240,
Iodine value 2.8, hydroxyl value 50) (trade name; Polytail HA, manufactured by Mitsubishi Chemical Corporation) 0.1 mol, ethylene glycol 0.5 mol (2,2'-butylethylpropane diol: hydrogenated polybutadiene polyol: ethylene Glycol = 28: 67: 5 (weight ratio), and zinc acetate 2.0 × 10 ⁻⁴ mol / acid as catalyst, antimony trioxide 3.0
An esterification reaction was carried out by charging x10 ^-4 mol / acid and melting and heating at 240 ° C in a nitrogen atmosphere. Then, tetra n-butyl titanate (1 × 10 ⁻⁴ mol / acid) was added, and 1
Polycondensation was performed at 250 ° C. for 1 hour under Torr to obtain polyester resin (I) (molecular weight 5000, glass transition temperature (Tg) -25 ° C.). The polyester resin (I)
Was transparent and had excellent compatibility.

100 g of the polyester resin (I)
0.04 mol of isophorone diisocyanate was added to (0.02 mol), and the mixture was stirred at 80 ° C. under normal pressure for 8 hours. 2-Hydroxyethyl acrylate was added in an amount of 0.04 mol and stirred at 60 ° C. for 6 hours to carry out a reaction to obtain a urethane (meth) acrylate resin (II). (Molecular weight 6
100, glass transition temperature (Tg) -31 ° C). 100 parts of the obtained urethane (meth) acrylate resin (II) was mixed with 4 parts of 2-hydroxy-2-methylphenylpropanone (trade name: Darocur-1173, manufactured by Merck Ltd.) as a sensitizer. A resin composition was obtained. With respect to the resin composition, the transparency, adhesion, and
The curability was evaluated.

(Transparency) 7 g of the resin composition was placed in an 8 ml glass bottle, the light transmittance was measured, and the state in which nothing was placed was evaluated as 100%.

(Adhesion) polypropylene plate (thickness: 2 m
m, width 70 mm, length 150 mm), the heat-melted resin composition was applied by a bar coater to a thickness of 30 μm, and this was applied at a height of 20 cm using a high pressure mercury lamp of 80 w / cm. Feed rate 5m /
UV irradiation was performed under the condition of min. Regarding the adhesion of the obtained coating film, (1) the adhesiveness of the cellophane tape peeling tape of the 1 mm square immediately after irradiation and (2) the adhesiveness of the cellophane tape peeling tape of the 1 mm square after soaking in 80 ° C warm water for 24 hours were evaluated. did.

(Curability) After the same ultraviolet irradiation as above,
The presence or absence of tackiness was examined by applying a finger to the obtained coating film and evaluated according to the following criteria. A: There is no tackiness at all. B: There is some tackiness. C: There is a feeling of tack.

Example 2 Polyester resin (I) was obtained in the same manner as in Example 1 except that the acid component and glycol component shown in Table 1 were used (molecular weight 5200, glass transition temperature (T
g) -50 ° C). The polyester resin was transparent and excellent in compatibility. The obtained polyester resin (I) is treated in the same manner as in Example 1 to obtain a urethane (meth) acrylate resin (II) (molecular weight 6100, glass transition temperature (Tg) -56 ° C.), and a sensitizer is further added. Then, a resin composition was obtained. The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1.

Example 3 Polyester resin (I) was obtained in the same manner as in Example 1 except that the acid component and glycol component shown in Table 1 were used (molecular weight 5000, glass transition temperature (T
g) -29 ° C). The polyester resin was transparent and excellent in compatibility. The obtained polyester resin (I) is treated in the same manner as in Example 1 to obtain a urethane (meth) acrylate resin (II) (molecular weight 5900, glass transition temperature (Tg) -35 ° C), and further a sensitizer is added. Then, a resin composition was obtained. The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1.

Example 4 In Example 1, 100 parts of urethane (meth) acrylate resin (II) was added to 2-hydroxy-2 as a sensitizer.
-Methylphenylpropanone (trade name: Darocur-1
173, manufactured by Merck & Co., Inc.), and 20 parts of 2,2'-butylethylpropanediol diacrylate and 20 parts of trimethylolpropane triacrylate as reactive diluents were further added in the same manner as above, and a resin composition was prepared. Obtained. The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1.

Comparative Example 1 A polyester resin was obtained in the same manner as in Example 1 except that the acid component and glycol component shown in Table 1 were used (molecular weight 5200, glass transition temperature (Tg) -3).
1 ° C). The polyester resin became cloudy, resulting in poor compatibility. The obtained polyester resin is treated in the same manner as in Example 1 to obtain a urethane (meth) acrylate resin (molecular weight 6200, glass transition temperature (Tg) -37.
C.) and a sensitizer were further added to obtain a resin composition. The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1.

Comparative Example 2 A polyester resin was obtained in the same manner as in Example 1 except that the acid component and glycol component shown in Table 1 were used (molecular weight 5100, glass transition temperature (Tg) 15).
° C). The polyester resin was transparent and had excellent compatibility. The obtained polyester-based resin is treated in the same manner as in Example 1 to obtain a urethane (meth) acrylate-based resin (molecular weight 6000, glass transition temperature (Tg) 7 ° C.), and a sensitizer is further added to obtain a resin composition. It was The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1.

Comparative Example 3 A polyester resin was obtained in the same manner as in Example 1 except that the acid component and glycol component shown in Table 1 were used (molecular weight 4900, glass transition temperature (Tg) -3).
4 ° C). The polyester resin became cloudy and had poor compatibility. The obtained polyester resin is treated in the same manner as in Example 1 to obtain a urethane (meth) acrylate resin (molecular weight 5900, glass transition temperature (Tg) -39).
C.) and a sensitizer were further added to obtain a resin composition. The resin composition was evaluated for transparency, adhesion and curability in the same manner as in Example 1. Table 2 shows the evaluation results of the examples and the comparative examples.

[0040]

[Table 1] Acid component Glycol component (a-1) (a-2) (a-3) (b-1) (b-2) Other glycol component (%) (%) (%) (%) ( %) (%) Example 1 DDA IPA-BEPG PTHA EG (28) (72) (28) (67) (5) 〃 2 DDA − − BEPG PTHA EG (100) (28) (67) (5) 〃 3 DDA IPA DA BEPG PTHA EG (40) (33) (27) (28) (67) (5) 〃 4 DDA IPA-BEPG PTHA EG (28) (72) (28) (67) (5) Comparative Example 1 DDA IPA --- PTHA EG NPG (28) (72) (74) (7) (19) 〃 2 DDA IPA-BEPG-EG (28) (72) (82) (18) 〃 3 DDA IPA DA-PTHA EG (40 ) (33) (27) (74) (7)

Note) The symbols in the table are as follows. (A-1): Aliphatic dicarboxylic acid (a-2): Aromatic dicarboxylic acid (a-3): Branched polybasic acid having an alkyl group having 2 or more carbon atoms in its side chain (b-1): Number of carbon atoms Branched diol having 2 or more alkyl groups in the side chain (b-2): Hydrogenated polybutadiene polyol (%): In the acid component, the weight% of each component relative to the entire acid component. % By weight DDA: dodecanedicarboxylic acid, IPA: isophthalic acid, DA: hydrogenated product of dimer acid, BEPG: 2,2′-
Butylethylpropanediol, PTHA: Polytail HA (manufactured by Mitsubishi Chemical Corporation), EG: Ethylene glycol, N
PG: Neopentyl glycol

[0042]

[Table 2] Transparency Adhesion Curability (1) (2) (UV irradiation frequency) Example 1 47 100/100 100/100 A (2 times) 〃 2 63 100/100 100/100 B (5 times) 〃 3 45 100/100 100/100 A (4 times) 〃 4 31 100/100 100/100 A (1 time) Comparative Example 1 0 100/100 50/100 C (5 times) 〃 2 47 0/100 0 / 100 A (twice) 〃 30 80/100 50/100 C (five times) Note) The adhesion value is the residual rate of the coating film.

Example 5 Urethane (meth) acrylate resin (II) of Example 1
To 100 parts, 4 parts of a sensitizer 2-hydroxy-2-methylphenylpropanone (trade name: Darocur-1173, manufactured by Merck & Co., Inc.) was mixed to obtain a resin composition. A polyethylene terephthalate film (thickness 20
μm) so as to have a thickness of 70 μm, and a polypropylene plate (thickness: 2 mm, width 70 mm, length:
150 mm) were bonded together at 20 ° C. under conditions of 0.3 kg / cm ² and 10 seconds, irradiated with ultraviolet rays, and the adhesive force after that was measured by the following method. Ultraviolet irradiation was performed under the conditions of 80 w / cm × 20 cm × 5 m / min, as in the above.

(Adhesive strength) Using a Shimadzu Autograph AG-100 under the conditions of 20 ° C. and 65% RH, a pulling speed of 1
Width of adhesive surface at 00 mm / min 1 per inch
An 80-degree peel test was performed to measure the adhesive force.

Comparative Example 4 Urethane (meth) acrylate resin (II) of Comparative Example 2
Was used in the same manner as in Example 5 to measure the adhesive force.
Table 3 shows the measurement results.

[0046]

[Table 3] Urethane (meth) acrylate resin (II) Adhesion (g / inch) Example 5 Example 1 1190 Comparative Example 4 Comparative Example 2 140

[0047]

EFFECT OF THE INVENTION The active energy ray-curable photocurable resin composition of the present invention, which comprises a polyester resin, exhibits excellent adhesiveness (adhesiveness) to a polyolefin resin, and further has transparency and curing. Due to its excellent properties, it is effectively used for applications such as adhesives, paints, and coatings.

Claims (8)

[Claims] 1. A polybasic acid (A) as an acid component, which has 2 carbon atoms.
Branched diol (b-1) having the above alkyl group in the side chain
And a hydroxyl group-containing (meth) acrylate (D) after adding a diisocyanate compound (C) to a polyester resin (I) obtained by polycondensing a hydrogenated polybutadiene polyol (b-2) as a glycol component (B). Urethane (meth) acrylate resin (I
A photocurable resin composition comprising I) and a sensitizer (III). 2. As the polybasic acid (A), an aliphatic dicarboxylic acid (a-1) having at least 2 to 20 carbon atoms, or an aliphatic dicarboxylic acid (a-1) having at least 2 to 20 carbon atoms.
And an aromatic dicarboxylic acid (a-2), having 2 to 2 carbon atoms.
The compounding ratio of 20 aliphatic dicarboxylic acid (a-1) and aromatic dicarboxylic acid (a-2) is 10:90 to 100: 0.
It is (weight ratio), The photocurable resin composition of Claim 1 characterized by the above-mentioned. 3. A branched polybasic acid (a-) having a side chain of an alkyl group having at least 2 carbon atoms as the polybasic acid (A).
3. The photocurable resin composition according to claim 1 or 2, wherein the photocurable resin composition comprises 3). 4. The compounding amount of the sensitizer (III) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the urethane (meth) acrylate resin (II).
3. The photocurable resin composition according to any one of 3 above. 5. The photocurable resin composition according to claim 1, further comprising a reactive diluent (IV). 6. The blending ratio of the urethane (meth) acrylate resin (II) and the reactive diluent (IV) is 95: 5.
It is 5:95 (weight ratio), The photocurable resin composition of Claim 5 characterized by the above-mentioned. 7. A coating material comprising the photocurable resin composition according to claim 1. 8. An adhesive comprising the photocurable resin composition according to claim 1.