JPH0380252A - Photosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosetting resin compsn. having satisfactory adhesive property to a polyester molded product and ensuring flexibility after setting by blending a reactive diluent having at least one acryloyl group in one molecule with a compd. having a specified structure at a terminal of thermoplatic polyester. CONSTITUTION:The reactive diluent of 5-95 pts. wt. having at least one acryloyl group in one molecule is blended with the compd. of 95-5 pts. wt. having a structure represented by formula I (where R is H or 1-5C alkyl) at a terminal of thermoplatic polyester having 2,000-20,000 number average mol. wt. to obtain the photosetting resin compsn. The compsn. is easily photoset, has satisfactory adhesive property to polyester and ensures improved flexibility after setting.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photocurable resin composition, and specifically, a photocurable resin composition that has good adhesion to polyester molded products and excellent flexibility even after curing. The present invention relates to photocurable resin compositions that can be used in a wide range of applications such as paints, inks, adhesives, and coatings.

(Conventional technology) Polyester has excellent mechanical properties and heat resistance.

Because it has weather resistance and chemical resistance, it is widely used as a material for various molded products such as fibers, films, and sheets. In addition, in recent years, due to the trend toward composites, opportunities for using polyesters in combination with each other or with other resins have increased, and in this case, adhesion to the polyester resin is an essential condition.

On the other hand, photocurable resin saves energy and resources.

It has advantages in terms of space saving and environmental pollution control. Therefore, research and development of various photocurable resins has been actively carried out depending on the application, and performance according to each application has been required. One of them is for polyester molded products.

1 for conventional photocurable resins mainly based on acrylic resins.
Since the acryloyl group and methacryloyl group necessary for polymerization and curing lack affinity for polyester, the wettability and adhesion to polyester were poor. Furthermore, methylene chains produced by polymerization and curing of acryloyl groups and methacryloyl groups also lacked affinity for polyester, resulting in poor wettability and adhesion to polyester. Even if acrylic ester has a low concentration of acryloyl groups and has a relative affinity for polyester, its adhesion to polyester will decrease if it is cured by single polymerization, so in order to obtain sufficient adhesive performance for polyester, polyester It was necessary to pre-treat the surface by applying a primer on it. Moreover, since the flexibility of photocurable resins mainly composed of acrylic esters decreases when cured, there is a risk that peeling or cracking may occur when applied to flexible polyester molded products.

(Problems to be Solved by the Invention) In view of the above circumstances, one object of the present invention is to have good adhesion, especially to polyester molded products.

An object of the present invention is to provide a photocurable resin composition that remains flexible even after curing.

(Means for Solving the Problems) As a result of intensive studies on the above-mentioned problems, the present inventors found that a photocurable resin composition having the component composition described below is easily cured by light and has good properties against polyester. The present invention was achieved based on the knowledge that the adhesive exhibits good adhesion and also has good flexibility even after curing.

That is, the gist of the present invention is as follows.

5 to 95 parts by weight of a reactive diluent having at least one acryloyl group or methacryloyl group per molecule and at least a portion of the terminal or side chain of a thermoplastic polyester having a number average molecular weight of 2.000 to 20.000. below (
1) A photocurable resin composition comprising 95 to 5 parts by weight of a compound having a structure represented by the formula:

OH0 (However, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.) What is the reactive diluent having at least one acryloyl group or methacryloyl group per molecule used in the present invention?2Usually photocuring reaction A compound used in the field of 1 reactivity, and.

It acts like a solvent. For example, acrylates are preferably used, and specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate , lauryl acrylate, lauryl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate), ECH (epichlorohydrin)
Modified bisphenol A diacrylate, EO (ethylene oxide) modified bisphenol A dianorelay), E
O-modified bisphenol S diacrylate, bisphenol A dimethacrylate, E○-modified bisphenol A dimethacrylate, 1,4-butanediol diacrylate)
, 1.4-butanediol dimethacrylate, butoxyethyl acrylate, butoxyethyl methacrylate),
ECH modified butyl acrylate, 1゜3-butylene glycol diacrylate, 1.3-butylene glycol dimethacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyl acrylate, E○ modified dicyclopentenyl acrylate, E○ modified dicyclopentenyl methacrylate, diethylene glycol diacrylate.

diethylene glycol dimethacrylate, ECH modified diethylene glycol dimethacrylate, ethyl diethylene glycol acrylate), ECH modified ethylene glycol diacrylate, ethylene glycol dimethacrylate, ECH modified ethylene glycol dimethacrylate, 2-ethylhexyl acrylate, 2-ethylhexylmethacjJ17-), Glycerol acrylate/methacrylate, glycerol methacrylate, glycerol dimethacrylate, glycidyl acrylate.

glycidyl methacrylate), 1,6-hexanethiol diacrylate), ECH-modified 1,6-hexane diacrylate), 1,6-hexanethiol dimethacrylate,
2-Hydroxyethyl acrylate.

2-hydroxyethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate.

Caprolactone-modified 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate.

2-hydroxypropyl methacrylate, isobornyl acrylate, isobornyl methacrylate, isodecyl acrylate, isooctyl acrylate, 2-methoxyethyl acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate.

Methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol 400 methacrylate,
Methoxydipropylene glycol acrylate, methoxylated cyclodecatriene acrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate.

Neopentyl glycol dimethacrylate, hydroxypivalic acid ester neopentyl glycol diacrylate, caprolactone-modified hydroxyhyvalic acid ester neopentyl glycol diacrylate, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polypropylene glycol acrylate, EC
H-modified phenoxy acrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate.

Phenoxyhexaethylene glycol acrylate, phenyl methacrylate, EO-modified phthalic acid acrylate, caprolactone-modified phthalic acid diacrylate, polyethylene glycol 200 diacrylate, polyethylene glycol 400 diacrylate, polyethylene glycol 600 diacrylate, polyethylene glycol 9
0 methacrylate.

Polyethylene glycol 200 methacrylate, polyethylene glycol 400 methacrylate, polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, polyethylene glycol 600 dimethacrylate, polypropylene glycol 400 diacrylate, polypropylene glycol 30
0 methacrylate, polypropylene glycol 500 methacrylate, polypropylene glycol 800 methacrylate, polypropylene glycol 400 dimethacrylate, ECH modified propylene glycol diacrylate.

Stearyl acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl acrylate, triethylene glycol diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, tripropylene Examples include glycol diacrylate. In addition.

In the compound, the hydrogen atom bonded to the carbon atom is
It may be substituted with a halogen atom such as chlorine or fluorine, an alkyl group such as a methyl group, an alkoxy group, or other functional group. Furthermore, one or more of these compounds can be used in appropriate combination.

Next, a compound having a structure represented by the following formula (1) in at least a part of the terminal or side chain of a thermoplastic polyester having a number average molecular weight of 2.000 to 20.000 will be described.

(However, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.) This compound is produced by the reaction between the terminal or side chain carboxyl group of the thermoplastic polyester and the glycidyl acrylate represented by the following formula (2). can get.

The thermoplastic polyester is terephthalic acid.

Isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid.

Dicarboxylic acids such as 1.9-nonanedicarboxylic acid, 1.10-decanedicarboxylic acid, 1,2-dodecanedicarboxylic acid, 1.2-octadecanedicarboxylic acid, icosanedicarboxylic acid, cyclohexanedicarboxylic acid, hexahydrophthalic acid, etc. Ingredients: Oxyacid components such as malic acid, tartaric acid, 1,2-hydroxystearic acid, paraoxybenzoic acid, ε-oxycaproic acid (ε-caprolactone), ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol , ■, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-bentanediol, 1,6-hexanediol, l,9-nonanediol, 1.10-decanediol, Neopentyl glycol, 2.2.4-
It is obtained by appropriately combining glycol components such as trimethylpentane-■ and 3-diol, and in addition to the above components, trimellitic acid, pyromellitic acid, and trimethylol in an amount that does not cause so-called gelled products. Polyhydric carboxylic acids and polyhydric alcohol components such as ethane, trimethylolpropane, glycerin, and pentanylthritol, as well as dicarboxylic acids and glycols with unsaturated groups,
For example, those obtained by appropriately combining maleic acid, itaconic acid, etc. can be mentioned. Among the polyester components that make up thermoplastic polyester.

Acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, aliphatic dicarboxylic acids with a methylene group having 2 to 20 carbon atoms, trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride. polybasic acids and their anhydrides, aliphatic glycols with a methylene base of 2 to 20 carbon atoms as an alcohol component, or aliphatic oxyacids with a methylene base of 2 to 20 carbons as an oxyacid component (their lactones) In particular, those containing 5 to 70 mol%, more preferably 5 to 35 mol%, of aliphatic oxyacids or their lactones as a copolymer component are good for polyester molded products. It exhibits good adhesion and good flexibility after curing. This is because aliphatic oxyacids or their lactones cause the thermoplastic copolyester to lose its crystallinity at a relatively small copolymerization composition ratio. Further, the polyester has good compatibility with a reactive diluent having at least one acryloyl group or methacryloyl group per molecule, which is another component constituting the photocurable resin composition of the present invention. Regarding compatibility, copolymerization components containing polyfunctional monomers such as trimellitic acid and pyromellitic acid have a
The compatibility increases as the number of acryloyl or methacryloyl groups per molecule increases.

Furthermore, in the alcohol component that makes up polyester,
Molecular weight 500, such as polytetramethylene glycol
Copolymerizing polyalkylene glycols of about 1.500 to give elastic polyester properties, or creating products with aromatic rings such as ethylene oxide adducts to bisphenol and ethylene oxide adducts to bisphenol S. When glycol is copolymerized,
A cured composition with good heat resistance and adhesion can be obtained.

What are the properties of the photocurable resin composition of the present invention after curing?

It is greatly influenced by the properties of the thermoplastic copolyester, and can be controlled to some extent by changing the copolymer composition of the thermoplastic copolyester as described above, but in addition, the glass transition temperature (Tg) is -40 to 60
C., preferably -20 to 40.degree. C., the flexibility is further improved.

9 In the present invention, the number average molecular weight of the thermoplastic polyester residue in the thermoplastic polyester is 2.000.
~20.000. The requirement is preferably 3.000 to 9.000. If the ester chain forming the thermoplastic polyester is long to some extent, as in the present invention, if the average molecular weight is less than 2.000, strength, flexibility, etc. will not be exhibited, and if it is greater than 2,000, preferably 3.000 or more. At this time, it becomes possible to effectively control the properties of a composition after curing. Also, the average molecular weight is 2
If it is larger than 0.000, the viscosity of the composition becomes high, making it difficult to handle. 20. [It is preferable to use one with a value of 100 or less, more preferably 9,000 or less.

By regulating the thermoplastic polyester as described above, a photocurable resin composition with good adhesion and flexibility can be obtained.
It is preferable to decide according to the type and mixing ratio of the reactive diluent having at least one acryloyl group or methacryloyl group per molecule of the two components.

There are various methods for adjusting the carboxyl group weight and molecular weight of thermoplastic polyester. The most preferable method is to produce a high molecular weight polyester and depolymerize it with a predetermined amount of dicarboxylic acid or tricarboxylic acid. This is the way to get it. When this method is adopted, carboxyl groups and molecular weight can be easily controlled.

Examples of glycidyl acrylates include glycidyl acrylate, glycidyl methacrylate, and glycidyl methacrylate.

This reaction is carried out in bulk or in a diluent or organic solvent at a temperature below 120°C, preferably below 110°C. At temperatures exceeding 120°C, there is a risk that acryloyl groups and methacryloyl groups will undergo addition polymerization. A small amount of radical scavenger may also be used to prevent addition polymerization. In some cases, acids, bases, anion exchange resins,
A quaternary ammonium salt or the like is used as a catalyst.

Note that as the diluent, a low-viscosity compound having an acryloyl group or a methacryloyl group as shown in the example above can be used, and as an organic solvent, benzene, toluene, xylene, acetone, methyl ethyl ketone that can dissolve polyester can be used. , methyl isobutyl ketone, tetrahydrofuran, dioxane, cyclohexanone, ethyl acetate.

One or more types selected from methyl acetate, cellosolves, methylene chloride, chloroform, trichloroethane, tetrachloroethane, etc. can be used.

The photocurable resin composition of the present invention is prepared by adding 5 to 95 parts by weight of a reactive diluent having at least one acryloyl group or methacryloyl group per molecule, and (
1) 95 to 5 parts by weight of a compound having a structure represented by the formula,
More preferably, it consists of 90 to 10 parts by weight, and if the amount of the compound having the structure represented by formula (1) is less than 5 parts by weight, a product with excellent adhesiveness and flexibility after curing cannot be obtained. If the amount exceeds 95 parts by weight, photocuring becomes difficult.

In addition, in the present invention, the viscosity of the photocurable resin composition can be varied over a wide range depending on the amount of the compound having the structure represented by formula (1) mixed.

Depending on the purpose and use, an appropriate one can be put to practical use.

The photocurable resin composition of the present invention can be heated as it is.

Easily polymerized and cured by light, electron beams, catalysts, etc.

It can also be used in combination with the organic solvent or reactive diluent mentioned above.

In the present invention, the use of a photopolymerization initiator facilitates photopolymerization, and any photopolymerization initiator can be used as long as it can initiate photopolymerization of the photocurable resin composition. It can be appropriately selected depending on the composition ratio, light source, etc. Such photoinitiators include 1
For example, acetophenones, benzophenone, Michler's ketone.

Examples include benzyl and its derivatives, benzoin and its alkyl ethers, xanthone and its derivatives, thioxanthone and its derivatives, disphite compounds, azo compounds, and the like.

At this time, the wavelength of the irradiated light is usually 180 to 700.
nm is used. Irradiation with ultraviolet light is particularly effective. In addition, radiation such as a He-N'e laser, an Ar laser, various electron beams, and various X-rays can also be used, and curing can also be performed with heat or a catalyst.

In this case, the use of a sensitizer is extremely effective and enhances the practicality of the present invention by accelerating the photopolymerization rate caused by the pre-distributive polymerization initiator. As such a sensitizer.

For example, the 9th order is used. Namely.

Amines include aliphatic amines and aromatic amines.

Examples of nitrogen heterocyclic compounds and ureas include allyl urea and 〇-tolylthiourea; examples of sulfur compounds include sodium diethyldithiophosphate and soluble salts of aromatic sulfinic acids; examples of nitriles include N,N-disubstituted- p-
As aminobenzonitrile compounds and phosphorus compounds,
) IJ-n-butylphosphine and other nitrogen compounds.

As the N-nitrosohydroxylamine derivative, oxazoline compound, and chlorine compound, carbon tetrachloride, hexachloroethane, etc. are used.

The above-mentioned photopolymerization initiator and sensitizer are each 0 to 10 polymerized parts and 0 to 15 parts by weight, more preferably 0.5 to 15 parts by weight, respectively, per 100 parts by weight of the photocurable resin composition of the present invention. 2 parts by weight and O to 5 parts by weight are blended. One or more of these can be used in appropriate combinations from among those shown in specific examples.

Furthermore, in the photocurable resin composition according to the present invention,
In addition to the above ingredients, add 9 coloring agents if necessary.

It is possible to incorporate additives such as inorganic fillers.

The photocurable resin composition of the present invention can be used as it is, or by dissolving it in a solvent or diluent and adding various additives to form inks, paints, adhesives, surface coating materials, and plate-making materials.

Used in various fields as sealants, electrical insulation materials, etc.

It can be used effectively and has great industrial value.

(Example) The present invention will be specifically explained below by referring to an example. Note that "%" and "part" are based on weight, and "mole" indicates the molar ratio at the time of preparation.

Example 1 (1) Place the raw materials listed in Table 1 into an ester reaction tube.

Esterification was carried out at 250° C. for 2 hours while passing N and gas under normal pressure and flowing out the condensed water, and then polycondensation was carried out for 1 to 2 hours under 0.5 torr to obtain high molecular weight thermoplastic polyesters A and B. , C was obtained.

Table 1 [Unit: moles] The obtained thermoplastic polyesters were depolymerized with aliphatic dicarboxylic acids in the amounts shown in Table 2 at 250°C for 1 hour to form polyesters A-1, B-1 to 5. C-1 was obtained. The number average molecular weight was determined by end group titration. Also 1
In the table, the n value is the number of structures expressed by the above formula (1) and is an approximate value.

Table 2 (2) Polyester A-1, B-1 to 5. 100 parts of each of C-1 were dissolved in 100 parts of toluene, and mixed with glycidyl methacrylate at 100°C to give an acid value of 0.5 mg K○H/
The reaction was allowed to take place until the amount decreased to below g. 0.003 part of methoquinone was added as a thermal polymerization inhibitor, and 0.2 part of trimethylbenzylammonium chloride was added as a catalyst. After the reaction is complete,
Toluene was distilled off and the residue was dried under reduced pressure.

(3) The product obtained in (2) above was mixed with ECH-modified phenoxy acrylate at a ratio of 10%, 20%, and 30% to obtain a photocurable resin composition. 1 part of benzoin isopropyl ether and 2 parts of diethylaminoethyl methacrylate per 100 parts of the obtained photocurable resin composition.
The resulting film was sandwiched between PET films with one surface untreated, and irradiated with a metal halide lamp at 2000 mJ/cd to cure and adhere the PET films.The adhesion to PET was measured by T-peel strength. The results are shown in Table 3.

Example 2 Polyester A-1, B-1 to B-5, C- obtained in Example 1
1 was mixed with ECH-modified phenoxy acrylate in IO%, 20%, and 30%, respectively, and reacted with glycidyl methacrylate at 100°C until the acid value became 0.5 mgKOH/g or less. Methoquinone 0.0% as a thermal polymerization inhibitor.
0.003 parts and 0.2 parts of trimethylbenzylammonium chloride as a catalyst were added.

After the reaction was completed, the resulting photocurable resin composition was measured for adhesion to PET in the same manner as in Example 1.

The results are shown in Table 4.

Example 3 Resin A-1゜8-2~ used for adhesion test in Example 2
5. B Y K per 100 parts of resin for C-1
Add 1 part of -300 (manufactured by B Y K Chemika 1).

Coating a PET film with a thickness of about 100 μm and a metal halide lamp at 2000 m J/ctl
The samples were cured by irradiation and tested for flexibility by 180" bending. Table 5 shows the results.

Comparative Example 1 Polymer B in Table 1 was depolymerized with 15 mol % of ADA to obtain B-6 (number average molecular weight: 1100). B-
6 was reacted and treated in the same manner as in Examples 1 and 2.3 to obtain PET.
The adhesion was measured. The results are shown in Tables 3, 4, and 5 as comparative examples.

not glued) Table 4 [Unit: kg/25mm] * A is interfacial peeling.

(2) indicates inertial peeling in Table 5 (effects of the invention) The photocurable resin composition of the present invention has excellent adhesion to polyester molded products and remains flexible even after curing, resulting in peeling, cracking, etc. will not occur. Therefore, it can be widely used as paint 6 ink, adhesive, and coating agent. Note that, as a matter of course, the photocurable resin composition of the present invention.

Items other than polyester molded products 1 For example, it can be applied to metals, etc., and the photocurable resin composition of the present invention is coated on metal plates and the like.

Pre-forming process It can also be used as coated metal.

Claims (1)

[Claims] (1) 5 to 95 parts by weight of a reactive diluent having at least one acryloyl group or methacryloyl group per molecule and the terminal or side chain of a thermoplastic polyester having a number average molecular weight of 2,000 to 20,000. A photocurable resin composition comprising, at least in part, 95 to 5 parts by weight of a compound having a structure represented by the following formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, R represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)