KR102391701B1 - Active ray curable composition, active ray curable ink composition, and method of making the same - Google Patents

Abstract

[Solutions] An actinic ray-curable composition comprising (I) a vinyl chloride-based copolymer and (II) a photocurable monomer and/or an oligomer, wherein the (I) vinyl chloride-based copolymer comprises, as a structural unit, the following ( components a) to (d)
(a) 49 to 81 mass % of vinyl chloride units;
(b) 18 to 50 mass % of fatty acid vinyl units;
(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and
(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component
It relates to an actinic ray curable composition, an actinic ray curable ink composition, and a manufacturing method thereof, characterized in that it does not contain an organic solvent.
[Effect] The actinic ray curable composition and actinic ray curable ink composition of the present invention do not contain an organic solvent, have excellent flexibility, adhesion and thermal stability, and do not require a process of thermally drying the solvent during application or printing; There is less concern for the environment.

Description

Actinic ray curable composition, actinic ray curable ink composition, and their manufacturing method

The present invention relates to an actinic ray-curable composition containing a vinyl chloride-based copolymer, an actinic ray-curable ink composition, and a manufacturing method thereof.

Conventionally, actinic ray-curable compositions cured by active energy rays such as ultraviolet rays or electron beams have been used in paints, coatings, adhesives, printing inks, ink-receiving layers, printed circuit boards and electricity such as plastics, paper, glass, woodworking and inorganic materials. It has been put to practical use in various applications such as insulation. In particular, actinic light-curable inks are attracting attention because of their ability to record on a recording medium lacking in quick-drying properties or ink absorption properties.

It is calculated|required that such an actinic-ray-curable composition is excellent in a softness|flexibility and adhesiveness. For this reason, various methods for improving the flexibility and adhesiveness of the actinic ray-curable composition have been proposed so far.

For example, Japanese Patent Laid-Open No. 2010-006878 (Patent Document 1) discloses active energy in which active energy ray-curable ink is mixed with a varnish in which a thermoplastic resin having a glass transition temperature of 50 to 250° C. is dissolved in a solvent. A line curable ink composition is disclosed.

However, since this active energy ray-curable ink composition contains a solvent, the process of thermally drying a solvent becomes essential. Moreover, there is a possibility that a solvent may remain in the ink after printing, and the influence on the environment is also concerned.

On the other hand, as an actinic-ray-curable ink which does not contain a solvent, 0.3 mass % or more of the vinyl chloride-vinyl acetate type copolymer whose number average molecular weights are 14,000 or more and 25,000 or less in Unexamined-Japanese-Patent No. 2009-197156 (patent document 2). Cationic polymerization type inkjet ink containing 5.0 mass % or less is disclosed.

However, although the cationic polymerization type inkjet ink described in the said patent document 2 is said to be excellent in adhesiveness, there exists room for improvement. Moreover, the ink of the said patent document 2 also lacked flexibility, and was not suitable for the use which requires more flexibility.

In addition, it is important that the actinic-ray-curable composition used for various uses has little deterioration with time and is excellent in thermal stability.

Japanese Patent Laid-Open No. 2010-006878 Japanese Patent Laid-Open No. 2009-197156

The present invention has been made in view of the above circumstances, and it is to provide an actinic ray curable composition, an actinic ray curable ink composition, and a method for producing the same, which do not contain an organic solvent, are excellent in flexibility and adhesion, and are excellent in thermal stability. The purpose.

As a result of repeated studies to achieve the above object, the present inventors have obtained flexibility by dissolving a vinyl chloride-fatty acid vinyl-epoxy group-containing vinyl copolymer copolymerized with each unit in a specific ratio in a photocurable monomer and/or oligomer. , found that an actinic ray-curable composition excellent in adhesiveness and thermal stability could be obtained, leading to the achievement of the present invention.

Accordingly, the present invention provides the following actinic ray curable compositions, actinic ray curable ink compositions, and methods for producing them.

〔One〕

(I) a vinyl chloride-based copolymer, and (II) an actinic ray-curable composition containing a photocurable monomer and/or oligomer, wherein the (I) vinyl chloride-based copolymer comprises, as a structural unit, the following (a) to ( d) ingredients

(a) 49 to 81 mass % of vinyl chloride units;

(b) 18 to 50 mass % of fatty acid vinyl units;

(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and

(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component

It contains, and an actinic light curable composition characterized in that it does not contain an organic solvent.

〔2〕

The (II) photo-curable monomer and/or oligomer is a monofunctional acrylate, a bifunctional acrylate, a polyfunctional acrylate, a monofunctional methacrylate, a bifunctional methacrylate, a polyfunctional methacrylate and a urethane acrylate. The actinic light curable composition according to [1], which is one or two or more monomers selected from the group and/or an oligomer of the monomers.

[3]

The actinic-ray-curable composition as described in [1] or [2] whose content of the said vinyl chloride-type copolymer (I) is 1-30 mass % with respect to the whole actinic-ray-curable composition.

〔4〕

An actinic ray curable ink composition comprising the actinic ray curable composition according to any one of the above [1] to [3] and a pigment.

[5]

At least (a') a vinyl chloride monomer, (b') a fatty acid vinyl monomer, (c') an epoxy group-containing vinyl monomer, and, if necessary, components other than the above (a'), (b') and (c') components (d') a vinyl monomer is copolymerized, and during the copolymerization reaction, (a') a vinyl chloride monomer is further added, as a structural unit, the following (a) to (d) components

(a) 49 to 81 mass % of vinyl chloride units;

(b) 18 to 50 mass % of fatty acid vinyl units;

(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and

(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component

(I) to obtain a vinyl chloride copolymer containing The method for producing an actinic ray curable composition according to any one of the above [1] to [3], wherein the actinic ray curable composition is prepared.

[6]

The method for producing an actinic ray-curable composition according to [5], wherein the copolymerization reaction is carried out by suspension polymerization, and the (a') vinyl chloride monomer is further added after the temperature is raised.

[7]

A method for producing an actinic ray curable ink composition, wherein the active ray curable ink composition is obtained by dispersing a pigment in the actinic ray curable composition obtained by the production method according to the above [5] or [6].

The actinic-ray-curable composition and actinic-ray-curable ink composition of this invention do not contain an organic solvent, and are excellent in flexibility, adhesiveness, and thermal stability. Therefore, the process of thermally drying a solvent at the time of application|coating or printing is unnecessary, and there is little concern about the environment. In addition, since the composition of the present invention has excellent flexibility, adhesion and thermal stability, it can be widely used for various purposes.

The actinic-ray-curable composition of this invention, as a structural unit, following (a)-(d) component

(a) 49 to 81 mass % of vinyl chloride units;

(b) 18 to 50 mass % of fatty acid vinyl units;

(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and

(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component

(I) containing a vinyl chloride-based copolymer.

Here, (a) a vinyl chloride unit, (b) a fatty acid vinyl unit, (c) an epoxy group-containing vinyl unit, (d) each vinyl unit of a vinyl unit other than the above (a), (b) and (c) components, (I) units constituting the vinyl chloride copolymer, respectively (a') vinyl chloride monomer, (b') fatty acid vinyl monomer, (c') epoxy group-containing vinyl monomer, (d') above (a), ( It contains vinyl monomers other than b) and (c) components.

(a) A vinyl chloride unit provides toughness and high surface hardness to the coating film of an actinic-ray-curable composition. (I) The proportion of (a) vinyl chloride units in the vinyl chloride copolymer is 49 to 81 mass%, preferably 50 to 75 mass%. (a) When the proportion of the vinyl chloride unit is less than 49 mass %, the glass transition point of the (I) vinyl chloride copolymer becomes low and it becomes difficult to maintain the particle shape. Moreover, when it exceeds 81 mass %, the solubility of (I) vinyl chloride-type copolymer with respect to (II) a photocurable monomer and/or an oligomer will fall, and transparency of an actinic-ray-curable composition will fall.

(I) The ratio of the (b) fatty acid vinyl unit in a vinyl chloride type copolymer is 18-50 mass %, Preferably it is 25-50 mass %. (b) When the proportion of the fatty acid vinyl unit is less than 18% by mass, the solubility of the (I) vinyl chloride copolymer to the (II) photocurable monomer and/or oligomer decreases, and the transparency of the actinic ray-curable composition also decreases. Moreover, when the ratio of (b) fatty acid vinyl units exceeds 50 mass %, the glass transition point of (I) vinyl chloride type copolymer becomes low, and it becomes difficult to maintain a particle shape.

(b) Examples of the fatty acid vinyl unit include units such as vinyl acetate, vinyl monochloroacetate, vinyl propionate, vinyl versatate, vinyl laurate, vinyl stearate, and vinyl benzoate. In particular, vinyl acetate units are preferable. Do.

(I) The ratio of the vinyl unit containing an epoxy group in (I) vinyl chloride-type copolymer is 0.25-1.5 mass %, Preferably it is 0.4-0.9 mass %. (c) Thermal stability is inferior as the ratio of an epoxy group containing vinyl unit is less than 0.25 mass %, and it may color with time. Moreover, when it exceeds 1.5 mass %, the solubility of (I) vinyl chloride-type copolymer with respect to (II) a photocurable monomer and/or an oligomer will fall, and transparency of an actinic-ray-curable composition will fall.

(c) Examples of the epoxy group-containing vinyl unit include units such as methyl glycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, allyl phenol glycidyl ether and glycidyl methacrylate; , particularly preferably glycidyl methacrylate.

(I) The vinyl chloride-based copolymer may contain, as the component (d), vinyl units other than the components (a), (b) and (c) as necessary. As vinyl units other than the component (d), that is, components (a), (b) and (c), hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acryl Rate, polyethylene glycol polypropylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, glycerin monoallyl ether, hydroxyethyl vinyl ether, ethylene glycol monoallyl ether, hydroxybutyl vinyl ether, (meth) allyl alcohol , N-methylol (meth) acrylamide, epoxy group-containing vinyl, styrene, α-methyl styrene, acrylnitrile, methyl (meth) acrylate, ethyl (meth) acrylate, such as alkyl (meth) acrylates, acrylic acid, and units such as methacrylic acid, maleic anhydride, crotonic acid, itaconic acid, and vinylidene chloride. Two or more types of these units may be included.

In addition, as the component (d), vinyl units other than components (a), (b) and (c) are contained in (I) 0 to 10 mass by mass in the vinyl chloride copolymer, as long as the effects of the present invention are not impaired. It is preferable that it is contained in the ratio of %, and a more preferable ratio is 0.1-10 mass %.

(I) Although it does not specifically limit about the manufacturing method of a vinyl chloride-type copolymer, For example, At least (a') a vinyl chloride monomer, (b') a fatty acid vinyl monomer, (c') an epoxy group-containing vinyl monomer, , by copolymerizing (d') vinyl monomers other than the above (a'), (b') and (c') components as necessary, as a structural unit, 49 to 81 mass % of (a) vinyl chloride units; (b) 18 to 50 mass % of fatty acid vinyl units, (c) 0.25 to 1.5 mass % of epoxy group-containing vinyl units, (d) 0 to 0 to vinyl units other than the components (a), (b) and (c) (I) Vinyl chloride-type copolymer containing 10 mass % can be obtained.

In addition, although each monomer used as a raw material may be thrown in collectively before the start of a copolymerization reaction, there may be a monomer further added during a copolymerization reaction. It is preferable that the (a') vinyl chloride monomer used as a raw material is further added during the copolymerization reaction separately from the amount added before the start of the copolymerization reaction, and the (a') vinyl chloride monomer is further added after the temperature is raised. desirable. Moreover, it is preferable to set it as the quantity which further adds 40-80 mass % in the (a') vinyl chloride monomer used as a raw material. By doing in this way, the (I) vinyl chloride-type copolymer excellent in thermal stability and solubility with respect to (II) a photocurable monomer and/or an oligomer is obtained.

The above copolymerization reaction is preferably carried out by suspension polymerization. Specifically, after nitrogen substitution in the polymerization reactor, polymerization medium, suspending agent, polymerization initiator, (a') vinyl chloride monomer, (b') fatty acid vinyl monomer, (c') epoxy group-containing vinyl monomer, if necessary (d') vinyl monomers other than the components (a'), (b') and (c') are press-injected. Thereafter, the temperature is raised to an appropriate polymerization temperature, and the copolymerization reaction is initiated under a nitrogen atmosphere. During this copolymerization reaction, you may further add each monomer used as a raw material.

Examples of the suspending agent include cellulose derivatives such as polyvinyl alcohol, polyvinyl acetate partially saponified product, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, Synthetic polymers such as maleic acid-styrene copolymer and maleic acid-methylvinyl ether copolymer, natural polymers such as starch and gelatin, polyalkylene oxide such as polyethylene oxide and polypropylene oxide, oxyethylene-oxypropylene block copolymer, etc. can be heard These can also be used in combination of 2 or more type.

It is preferable that the weight average molecular weights of a suspension agent are 50,000-5 million. As suspension, polyalkylene oxide, such as polyethylene oxide and polypropylene oxide, can be used suitably, for example. Moreover, it is preferable that the usage-amount of a suspending agent is 0.05-0.3 mass % with respect to the total amount of a raw material monomer.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanol peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxy. Organic peroxides such as ethyl peroxydicarbonate, di-3-methoxybutylperoxydicarbonate, butylperoxyneodecanate, and di-3,5,5-trimethylhexanol peroxide, and azobisisobutyro Azo compounds, such as nitrile and 2, 2- azobis (2, 4- dimethyl) valeronitrile, etc. are mentioned. These can also be used in combination of 2 or more type. Moreover, it is preferable that the usage-amount of a polymerization initiator is 0.1-0.3 mass % with respect to the total amount of a raw material monomer.

As the polymerization medium, ion-exchanged water can be used. Moreover, what mixed water-soluble alcohol, such as methanol and isopropyl alcohol, in the ratio of 50 mass % or less in a polymerization medium can also be used. It is preferable that the usage-amount of a polymerization medium is 50-200 mass % with respect to the total amount of a raw material monomer.

In addition, (I) a chain transfer agent can also be used in the copolymerization reaction at the time of manufacture of a vinyl chloride type copolymer. As a chain transfer agent, the dihydrooxaphosphaphenanthrene type phosphorus compound which has a cyclic organophosphorus compound is preferable. It is preferable that the usage-amount is 0.3-0.6 mass % with respect to the total amount of a raw material monomer, More preferably, it is 0.4-0.5 mass %. When the usage-amount of a chain transfer agent is less than 0.3 mass %, there exists a tendency for the viscosity of an actinic-ray-curable composition to become high, handling is difficult and there exists a possibility that workability|operativity may worsen. Moreover, when the usage-amount of a chain transfer agent exceeds 0.6 mass %, the physical strength and durability of the coating film of an actinic-ray-curable composition may fall.

(I) In the copolymerization reaction at the time of production of a vinyl chloride-based copolymer, a suspending agent, a polymerization initiator, a chain transfer agent, etc. may be collectively added before the start of the copolymerization reaction, but may be added further during the copolymerization reaction. Moreover, it is preferable that polymerization temperature is 50-80 degreeC, More preferably, it is 55-75 degreeC.

The vinyl chloride-based copolymer (I) obtained by the above copolymerization reaction is preferably separated from the polymerization medium and dried to form a powder. About the average particle diameter of this vinyl chloride-type copolymer powder, it is preferable that it is 50-500 micrometers. In addition, this average particle diameter is a value measured using a laser diffraction/scattering type particle diameter distribution measuring apparatus, for example, LA-950V2 (made by Horiba).

(I) The average degree of polymerization of the vinyl chloride copolymer is preferably 150 to 800, more preferably 300 to 500. This average degree of polymerization is a value computed from the result of measuring the time required for the sample to fall at 30.0 degreeC with respect to the sample melt|dissolved in nitrobenzene using the Ubbelohde viscometer.

(I) The number average molecular weight of the vinyl chloride copolymer is preferably 20,000 or more, more preferably 25,000 or more. In addition, this number average molecular weight is a value measured using a molecular weight distribution measuring apparatus, for example, "GPC-900" by the JASCO company.

The actinic-ray-curable composition of this invention contains (I) a vinyl chloride-type copolymer, and (II) a photocurable monomer and/or an oligomer.

The photocurable monomer and/or oligomer as component (II) is a monomer and/or oligomer that can be polymerized and cured by light of a characteristic wavelength. As said component (II), it is especially preferable to superpose|polymerize and harden|cure with an ultraviolet-ray.

(II) The photocurable monomer and/or the oligomer is preferably radically polymerizable, although radical polymerization, cationic polymerization, and anionic polymerization are not considered. Such (II) photocurable monomers and/or oligomers include monofunctional acrylates, bifunctional acrylates, polyfunctional acrylates, monofunctional methacrylates, bifunctional methacrylates, polyfunctional methacrylates and urethane acrylates. It is preferable that it is 1 type or 2 or more types of monomers selected from the group of. Specifically, 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acrylo Iloxyethoxy) phenyl] fluorene, tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate (HDDA), 1,9-nonanediol diacrylate rate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (TPGDA), polytetramethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Polyethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecanedimethanol dimethacrylate, 1,10-decanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1, 9-nonanediol dimethacrylate, neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerin dimethacrylate, polypropylene glycol dimethacrylate, ethoxylated isocyanuric acid triacrylate , ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate (TMPTA), ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol Tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, etc. are mentioned. Moreover, the oligomer of these monomers may be sufficient. In this case, the oligomer generally has a degree of polymerization of 10 to 100.

It is preferable to make an actinic-ray-curable composition contain a photoinitiator with (II) a photocurable monomer and/or an oligomer. The photopolymerization initiator is one that generates active species by irradiation with light having a characteristic wavelength, and (II), depending on the type of the photocurable monomer and/or oligomer, suitable from a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator You can choose. In particular, it is preferable to use an optical radical polymerization initiator that generates radicals by ultraviolet rays. As such a photoinitiator, an alkylphenone type photoinitiator, an acylphosphine oxide type|system|group photoinitiator, an intramolecular hydrogen extraction type photoinitiator, an oxime ester type photoinitiator, etc. are mentioned. Among them, an alkylphenone-based photopolymerization initiator is preferable, and specifically, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy -2-Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2 -Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4- Methylthio phenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2- [(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; and the like. More preferably, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[ 4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy- Preference is given to 2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one. If it is a commercially available thing, IRUGACURE 184, 1173, 2959, 127 by BASF will be mentioned.

When the total amount of the (I) vinyl chloride copolymer and (II) photocurable monomer and/or oligomer is 100 mass parts, it is preferable to contain 1 mass part or more of a photoinitiator, More preferably, it is 1-10 mass is wealth If this content is less than 1 mass part, an actinic-ray-curable composition may not harden|cure.

An actinic-ray-curable composition can be obtained by dispersing and dissolving (I) a vinyl chloride-type copolymer in (II) a photocurable monomer and/or an oligomer. (I) The vinyl chloride copolymer is preferably contained in an amount of 1 to 30% by mass, more preferably 20% by mass, based on the total amount of the (I) vinyl chloride copolymer and (II) the photocurable monomer and/or oligomer. -30 mass %. (I) When content of a vinyl chloride-type copolymer is less than 1 mass %, in softness|flexibility, adhesiveness, thermal stability, etc., the desired effect may not fully be acquired. Moreover, when the said content exceeds 30 mass %, the (I) vinyl chloride-type copolymer may not melt|dissolve, or a viscosity may become high too much.

Moreover, about the temperature at the time of dispersing and dissolving (I) a vinyl chloride-type copolymer in (II) photocurable monomer and/or oligomer, it is suitable that it is 30-80 degreeC.

By dispersing and containing a pigment in an actinic-ray-curable composition, an actinic-ray-curable ink composition is obtained. As the pigment used, in the color index, Pigment White 4, Pigment White 6, Pigment White 21, Pigment Black 7 (Carbon Black), Pigment Blue 15, 15:1, 15:3, 15:4, 15:6, 60, Pigment Green 7 (chlorinated phthalocyanine green), 36 (brominated phthalocyanine green), Pigment Red 9, 48, 49, 52, 53, 57, 57:1, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, Pigment Violet 19, 23, 29, 30, 37, 40, 50, Pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, Pigments, such as 213 and pigment orange 36, 43, 51, 55, 59, 61, 71, 74, are mentioned.

Although the compounding quantity of a pigment is suitably selected according to the kind of pigment, Usually, it is the range of 10-20 mass parts with respect to 100 mass parts of actinic-ray-curable compositions.

A ball mill, a sand mill, an attritor, a roll mill, an agitator, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a wet jet mill, a paint shaker etc. can be used for dispersion|distribution of a pigment, for example.

About the actinic-ray-curable composition and actinic-ray-curable ink composition of this invention, for example, the spin coating method, the (doctor) knife coating method, the microgravure coating method, the direct gravure coating method, the offset gravure method, the reverse gravure method, the reverse roll It can apply on a base material by well-known methods, such as the coating method, the (Meyer) bar coating method, the die-coating method, the spray coating method, and the dip coating method.

Moreover, about the actinic-ray-curable composition and actinic-ray-curable ink composition of this invention, a coating film can be hardened by irradiating the light beam of a specific wavelength. In this case, it is preferable to employ|adopt an ultraviolet light as a light beam, and it is suitable for irradiation conditions to set it as irradiation intensity|strength 150-1,000 mJ/cm<2>, and making it into 1 to 300 second of irradiation time.

Although what is necessary is just to set the thickness of a coating film suitably according to the objective, from a viewpoint of price and performance, it is suitable that it is 0.5-200 micrometers, More preferably, it is 1.5-100 micrometers.

The actinic light curable composition and actinic light curable ink composition of the present invention are, for example, polyethylene terephthalate (PET), stretched polystyrene (OPS), stretched polypropylene (OPP), stretched nylon (ONy), polyvinyl chloride (PVC) , Polyethylene (PE), triacetyl cellulose (TAC), polycarbonate, acrylic resin, ABS, polyacetal, polyvinyl alcohol (PVA), rubber such as plastic, metal, paper, wood, glass, etc. can do.

The member formed with a coating film of the actinic ray curable composition or actinic ray curable ink composition on such a substrate is, for example, flooring, floor tiles, various plastic products, beverage cans, metal plates, printing papers, paper containers, record jackets, magazines, aluminum It is useful as vapor deposition paper, furniture, wall materials, building materials, optical applications, and the like.

Example

Hereinafter, a specific example is given and demonstrated about this invention. In addition, "part" in the following example shows "mass part".

[Production Example 1]

After nitrogen substitution in an autoclave equipped with a stirring device, 216 parts of deionized water, 53.6 parts of vinyl chloride monomer, 72 parts of vinyl acetate monomer, 0.9 parts of glycidyl methacrylate monomer, and polyethylene oxide (weight average molecular weight: 300,000) 0.72 parts, 0.09 parts of dibenzoyl peroxide and 0.09 parts of di-3,5,5-trimethylhexanol peroxide as a polymerization initiator were prepared.

Then, it heated up to 75 degreeC while stirring in nitrogen gas atmosphere, and 53.6 parts of vinyl chloride monomers were continuously press-in over 4.5 hours from immediately after reaching 75 degreeC, and the copolymerization reaction was advanced. When the autoclave internal pressure became 0.3 MPa, the residual pressure was cancelled|released, and it cooled and took out the resin slurry.

This resin slurry was filtered and dried to obtain a powdery (I) vinyl chloride-based copolymer. The structural unit of this (I) vinyl chloride copolymer is (a) 63.5 mass % of vinyl chloride unit, (b) 36.0 mass % of vinyl acetate unit, (c) 0.5 mass % of glycidyl methacrylate unit it was

About the obtained (I) vinyl chloride-type copolymer, the average degree of polymerization and number average molecular weight were measured by the method shown below. The results are shown in Table 1.

·Average degree of polymerization

(I) A sample is prepared by dissolving a vinyl chloride-based copolymer in nitrobenzene. About this sample, using the Ubbelode viscometer, the time required for the sample to fall at 30.0 degreeC is measured, and the average degree of polymerization is computed from the result.

・Number average molecular weight

(I) GPC-900 (manufactured by JASCO), separation column: KF-806M (manufactured by Shodex), KF-802 (manufactured by Shodex), A measurement is performed at the measurement temperature of 40 degreeC, and a number average molecular weight is computed from the result.

[Preparation Examples 2 to 4, Comparative Preparation Examples 1 and 2]

A vinyl chloride-based copolymer (I) described in Table 1 was obtained in the same manner as in Production Example 1 except that the amount of the vinyl chloride monomer, the vinyl acetate monomer, and the glycidyl methacrylate monomer was changed.

[Example 1]

30 parts of (I) vinyl chloride-based copolymer of Production Example 1 and (II) 70 parts of tripropylene glycol diacrylate were dissolved by stirring at 60°C for 1 hour. Furthermore, 5 parts of IRUGACURE 184 (made by BASF) was mixed at 60 degreeC for 20 minutes, and the actinic-ray-curable composition was obtained.

About the obtained actinic-ray-curable composition, haze value, crosscut, elongation, and thermal stability were measured by the method shown below, respectively. The results are shown in Table 2.

· Haze value

The actinic-ray-curable composition was apply|coated on the PET film (made by Cosmo Shine) using the bar coater #10, and the ultraviolet-ray of wavelength 365nm was irradiated for 2 minutes. The haze value of the film in which the coating film was formed was measured using the color difference and turbidity measuring instrument COH-400 (made by Nippon Denshoku Kogyo Co., Ltd.). It shows that transparency of a film is so high that a haze value is small. It is preferable that it is 3.0 or less, and, as for the haze value at the time of forming a coating film (film thickness after hardening: 12-20 micrometers) using bar coater #10, it is more preferable that it is 1.0 or less.

・Cross cut

The actinic-ray-curable composition was apply|coated on the PET film (made by Cosmo Shine) using the bar coater #5, and the ultraviolet-ray of wavelength 365nm was irradiated for 2 minutes. At this time, the film thickness after hardening will be 6-10 micrometers. 100 films in which the coating film was formed were cut into the square whose one side is 2 mm, and tape peeling was performed. Let the number of pieces peeled off as the measured value of the crosscut.

・Elongation

The actinic-ray-curable composition was apply|coated on the glass plate using the doctor knife 4mil, and the ultraviolet-ray of wavelength 365nm was irradiated for 3 minutes. The coating film peeled from the glass plate was cut|disconnected to width 15mm, and the sample was produced. About the produced sample, the tension test was done on the conditions of 10 mm/min using the tensile tester (made by NMB). The elongation and tensile strength of the coating film were calculated from the following formula. The elongation is required to be 5% or more.

Elongation = 100×ΔL/L [%]

Tensile force = F/S [kgf/㎟]

L: length of sample

S: cross-sectional area of the sample

ΔL: the length the sample is stretched until cut

F: Tensile force when the sample is elongated and cut by ΔL

· Thermal stability

The actinic-ray-curable composition was stored for 7 days in a 60 degreeC bath, and the color difference (DELTA)E in storage before and behind was measured using the color difference and turbidity measuring instrument COH-400 (made by Nippon Denshoku Kogyo Co., Ltd.). The value of the measured color difference (DELTA)E was made into the evaluation value of thermal stability.

[Example 2]

(I) The actinic-ray-curable composition of Table 2 was obtained by the method similar to Example 1 except having changed the (I) vinyl chloride-type copolymer of manufacture example 2 into (I) vinyl chloride-type copolymer.

[Example 3]

(I) The actinic-ray-curable composition of Table 2 was obtained by the method similar to Example 1 except having changed the (I) vinyl chloride-type copolymer into the (I) vinyl chloride-type copolymer of manufacture example 3.

[Example 4]

(I) The actinic-ray-curable composition of Table 2 was obtained by the method similar to Example 1 except having changed the (I) vinyl chloride-type copolymer into (I) vinyl chloride-type copolymer of manufacture example 4.

[Example 5]

(I) The content of the vinyl chloride-based copolymer was 20 parts by mass, and (II) the content of tripropylene glycol diacrylate was 80 parts by mass, in the same manner as in Example 1, except that the activity shown in Table 2 A light-curable composition was obtained.

[Comparative Example 1]

(II) 5 parts of IRUGACURE 184 (made by BASF) were mixed with 100 parts of tripropylene glycol diacrylates at 60 degreeC for 20 minutes, and the actinic-ray-curable composition of Table 2 was obtained.

[Comparative Example 2]

(I) The actinic-ray-curable composition of Table 2 was obtained by the method similar to Example 1 except having changed the (I) vinyl chloride-type copolymer to the (I) vinyl chloride-type copolymer of Comparative Production Example 1. .

[Comparative Example 3]

(I) The actinic-ray-curable composition of Table 2 was obtained by the method similar to Example 1 except having changed the (I) vinyl chloride-type copolymer to the (I) vinyl chloride-type copolymer of Comparative Production Example 2 .

In Examples 1 to 5 and Comparative Examples 1 to 3, according to the evaluation results of the haze value, crosscut, elongation, and thermal stability of each example, the actinic light curable composition of the present invention (Examples 1 to 5) has a haze value Since it was small, transparency was high, and since the value of a crosscut was also small, it turned out that it is excellent in adhesiveness. Moreover, the composition of this invention also has an elongation of 5 % or more, and is excellent also in flexibility. In addition, it was found that the composition of the present invention had a small color difference ΔE even before and after long-term storage at a high temperature, and was also excellent in thermal stability.

Claims (7)

(I) a vinyl chloride-based copolymer and (II) an actinic ray-curable composition containing a photocurable monomer and/or an oligomer, wherein the (I) vinyl chloride-based copolymer comprises, as a structural unit, the following (a) to ( d) ingredients
(a) 49 to 81 mass % of vinyl chloride units;
(b) 18 to 50 mass % of fatty acid vinyl units;
(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and
(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component
It contains and does not contain an organic solvent, The actinic light curable composition characterized by the above-mentioned. The method according to claim 1, wherein the (II) photo-curable monomer and/or oligomer is a monofunctional acrylate, a bifunctional acrylate, a polyfunctional acrylate, a monofunctional methacrylate, a bifunctional methacrylate, or a polyfunctional methacrylic. An actinic light curable composition which is one or two or more monomers selected from the group of acrylate and urethane acrylate and/or an oligomer of the monomer. The actinic-ray-curable composition of Claim 1 whose content of the said vinyl chloride-type copolymer (I) is 1-30 mass % with respect to the whole actinic-ray-curable composition. The actinic-ray-curable composition as described in any one of Claims 1-3, and an actinic-ray-curable ink composition characterized by containing the pigment. At least (a') a vinyl chloride monomer, (b') a fatty acid vinyl monomer, (c') an epoxy group-containing vinyl monomer, and, if necessary, components other than the above (a'), (b') and (c') components (d') a vinyl monomer is copolymerized, and during the copolymerization reaction, (a') a vinyl chloride monomer is further added, as a structural unit, the following (a) to (d) components
(a) 49 to 81 mass % of vinyl chloride units;
(b) 18 to 50 mass % of fatty acid vinyl units;
(c) 0.25 to 1.5 mass % of an epoxy group-containing vinyl unit, and
(d) 0-10 mass % of vinyl units other than said (a), (b) and (c) component
(I) to obtain a vinyl chloride copolymer containing The method for producing an actinic ray curable composition according to any one of claims 1 to 3, characterized in that the actinic ray curable composition is prepared. The method for producing an actinic ray-curable composition according to claim 5, wherein the copolymerization reaction is performed by suspension polymerization, and further addition of the vinyl chloride monomer (a') is performed after temperature rise. A method for producing an actinic ray curable ink composition comprising dispersing a pigment in the actinic ray curable composition obtained by the manufacturing method according to claim 5 to obtain an actinic ray curable ink composition.