JP7067228B2 - Structure manufacturing method - Google Patents

Description

The present invention relates to a method of manufacturing a structure by a jet printing method.

The jet printing method has been widely used in the production of printed matter. In recent years, jet printing type 3D printers have appeared, and their use in the production of three-dimensional objects is being considered.

As a method for manufacturing an article by the jet printing method, for example, a cured product (A) ink ejection step of ejecting ink droplets for forming a cured product (A) onto a substrate without connecting them to each other, and ejection are performed. The height difference between the cured product (A) forming step of curing the cured product (A) ink to obtain the cured product (A) and the cured product (A) for forming the cured product (B) is 1 μm or more. The cured product (B) ink ejection step of ejecting into the gap between the cured products (A) on the substrate and the curing of the ejected cured product (B) ink to obtain a cured product (B). The elastic modulus of the cured product (A) and the elastic modulus of the cured product (B) in the elastic modulus measurement by SPM as the cured product (A) ink and the (B) ink, including at least the product (B) forming step. A method for forming a structure is known, which comprises using an active energy curable ink having a modulus satisfying the relation of "elastic modulus of cured product (A)> elastic modulus of cured product (B)". (See, for example, Patent Document 1).

However, the structure obtained by the above method may not be sufficient in terms of adhesion and may not be sufficient in terms of production efficiency.

As a method for improving the adhesion of the structure, there are cases where it can be realized to some extent by changing the composition of the ink. However, when trying to improve the adhesion, the hardness of the cured product may be significantly reduced.

Japanese Unexamined Patent Publication No. 2016-215621

The problem to be solved by the present invention relates to a method for manufacturing a structure capable of efficiently manufacturing a structure having high hardness and excellent adhesion.

The present inventor jet-prints an active energy ray-curable composition set (A) composed of at least two types of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). In the step of coating in [1] and by irradiating the coated surface with active energy rays, the respective curing reactions of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). The above-mentioned problem is solved by a method for manufacturing a structure, which comprises a step [2] in which a part or all of the above is carried out in parallel.

According to the method for producing a structure of the present invention, a structure having high hardness and excellent adhesion can be obtained.

The figure obtained by observing the cured coating film of the structure obtained in Example 1 with a digital microscope VHX-600 at a magnification of 500 times is shown. The figure obtained by observing the cured coating film of the structure obtained in Comparative Example 1 with a digital microscope VHX-600 at a magnification of 500 times is shown.

The method for producing the structure of the present invention is an active energy ray-curable composition set (A) composed of at least two types of an active energy ray-curable composition (a1) and an active energy ray-curable composition (a2). [1] and the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) by irradiating the discharged region with active energy rays. ), It is characterized by having a step [2] in which a part or all of each curing reaction is carried out in parallel.

First, the step [1] will be described.

The step [1] is a step of ejecting the active energy ray-curable composition set (A) by a jet printing method.

As the active energy ray-curable composition set (A), a composition composed of at least two types of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) is used and is required. Depending on the situation, those composed of three or more kinds including other active energy ray-curable compositions can be used.

As the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2), those having different compositions or properties are selected and used in combination.

For example, as the combination of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2), the cured products have different hardness, different elastic moduli, and different surface tensions. Combinations, combinations with different colors, combinations with different refractive indexes, combinations with different hydrophilicity and hydrophobicity, combinations with different crystallinity, combinations with different acidity and basicity, combinations with different magnetism, conductivity and Examples thereof include combinations having different insulating properties, combinations having different densities, combinations having different glosses, and combinations having different adhesive strengths.

The combination of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) differs in terms of the presence / absence and content of inorganic components such as metals and organic components. , Combinations with different viscosities, etc. may be mentioned.

In the method for producing a structure of the present invention, as a combination of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2), one of the cured products is more than the other cured product. It is preferable to select a combination that is hard and has a higher adhesion than the one cured product in order to solve the above-mentioned problems.

The active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) include, for example, a monofunctional monomer having one functional group capable of reacting when irradiated with active energy rays, or the functional group. Those containing a polyfunctional monomer having two or more groups, a polymerization initiator, and an additive such as a colorant, if necessary, can be used.

Of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2), one of the cured products is harder than the other cured product, and the other cured product is cured by one. In the case of producing a structure having a higher adhesion than that of a product, the active energy ray-curable composition (a1) contains the monofunctional monomer more than the active energy ray-curable composition (a2). The cured product of the active energy ray-curable composition (a1) and the cured product of the active energy ray-curable composition (a2) can be used by using one having a high content and a low content ratio of the polyfunctional monomer. It is preferable for clarifying the difference in hardness and adhesion with the above. As described above, the active energy ray-curable composition (a1) having a high content ratio of the monofunctional monomer and a low content ratio of the polyfunctional monomer has a smaller hardness than the active energy ray-curable composition (a2). Form a cured product with high adhesion properties.

The active energy ray-curable composition (a1) contains 60% by mass or more of the monofunctional monomer with respect to the total amount of the polymerizable compound (A) contained in the active energy ray-curable composition (a1). It is preferable to use the one containing 70% by mass to 90% by mass, that is, the cured product of the active energy ray-curable composition (a1) and the active energy ray-curable composition. It is possible to clarify the difference in hardness and adhesion between the product (a2) and the cured product, and to form a cured product having a lower hardness and higher adhesion than the active energy ray-curable composition (a2). Especially preferable.

On the other hand, as the active energy ray-curable composition (a2), 60% by mass of the polyfunctional monomer is used with respect to the total amount of the polymerizable compound (A) contained in the active energy ray-curable composition (a2). It is preferable to use the one containing the above, and it is preferable to use the one contained in the range of 70% by mass to 90% by mass, that is, the cured product of the active energy ray-curable composition (a1) and the active energy ray-curing. A cured product having a property that the difference in hardness and adhesion between the sex composition (a2) and the cured product can be clarified, and the hardness is higher and the adhesion is lower than that of the active energy ray-curable composition (a1). Especially preferable for forming.

Examples of the monofunctional monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, and benzyl. Acrylate, methoxyethyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopen Teniloxyethyl acrylate, tetrahydrofurfuryl acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, acryloylmorpholine acrylate, N-acryloyloxyethyl hexahydrophthalimide acrylate, etc., N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylformamide, etc. alone or Two or more can be used in combination.

As the monofunctional monomer, it is more preferable to use a monomer such as phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, or N-vinylcaprolactam in order to further improve the adhesion. Further, in the case of further improving the hardness of the cured product, it is preferable to use a monomer such as isobornyl acrylate as the monofunctional monomer.

Examples of the polyfunctional monomer include 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1, 6-Hexanediol diacrylate, neopentyl glycol diacrylate, 1,8-octanediol diacrylate, 1,9-nonanediol diacrylate, tricyclodecanedimethanol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, propylene Glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, neopentyl glycol 1 mol with 4 mol or more of ethylene oxide or propylene oxide Diacrylate of diol obtained by addition, diacrylate of diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A, and addition of 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane. Diacrylate or triacrylate of triol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A, diacrylate of trimethylol propantriacrylate, pentaerythritol triacrylate, dipentaerythritol. Polyfunctional acrylates such as polyacrylates, ethylene oxide-modified phosphoric acid acrylates and ethylene oxide-modified alkyl phosphate acrylates, 2- (2-vinyloxyethoxy) ethyl acrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether. , Propylene glycol divinyl ether, Dipropylene glycol divinyl ether, Butanediol divinyl ether, Hexadiol divinyl ether, Cyclohexanedimethanol divinyl ether, Trimethylol propanetrivinyl ether and the like, preferably a polymerizable compound having 2 to 3 vinyl ether groups. Can be used alone or in combination of two or more.

As the polyfunctional monomer, it is preferable to use a polyfunctional monomer having a relatively high glass transition temperature or a polyfunctional monomer having a small curing shrinkage rate, and specifically, 1,6-hexanediol di. The use of acrylate, dipropylene glycol diacrylate, neopentyl glycol diacrylate, etc. has a viscosity at a level that can impart good ejection stability when printing by the jet printing method, and has high hardness and high adhesion. It is preferable to obtain an active energy ray-curable composition (a1) or (a2) capable of producing a structure having both properties.

The active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) include the monofunctional monomer and the polyfunctionality described above for the purpose of further improving the hardness of the structure of the present invention. Those containing a reactive oligomer in addition to the monomer can be used. As the reactive oligomer, for example, urethane acrylate oligomer, epoxy acrylate oligomer, polyester acrylate oligomer and the like can be used alone or in combination of two or more.

Moreover, it is preferable to use a photopolymerization initiator as the polymerization initiator.

When ultraviolet rays are used as active energy rays in the step [2] described later, a radical polymerization type photopolymerization initiator can be used as the photopolymerization initiator.

Examples of the radical polymerization type photopolymerization initiator include benzoin isobutyl ether, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide 6-trimethylbenzoyldiphenylphosphine. Oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1 -Hydroxycyclohexylphenylketone, benzoin ethyl ether, benzyldimethylketal, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 -On and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, benzophenone, 4-phenylbenzophenone, isophthalphenone, 4-benzoyl-4'-methyl-diphenylsulfide, etc. alone Alternatively, two or more types can be used in combination.

When an LED is used as the light source for emitting active energy rays, it is preferable to select a photopolymerization initiator corresponding to the peak wavelength of the light emitted from the LED, for example, 2-benzyl-2-. Dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- (4-morpholinophenyl) -butane- 1-on), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc. are used. can do.

As the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2), those containing additives can be used, if necessary, in addition to the above-mentioned ones.

Examples of the additive include trimethylamine, methyldimethylamine, triethanolamine, p-diethylaminoacetophenone, and p-dimethylamino in order to suppress the inactivation of radicals generated from the photopolymerization initiator by oxygen. Ethyl benzoate, isoamyl p-dimethylaminobenzoate, N, N-dimethylbenzylamine, 4,4'-bis (diethylamino) benzophenone and the like can be used.

Further, as the additive, a polymerization inhibitor can be used in order to improve the storage stability of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). As the polymerization inhibitor, for example, hydroquinone, methquinone, dit-butylhydroquinone, P-methoxyphenol, butylhydroxytoluene, nitrosamine salt and the like can also be used. The polymerization inhibitor is preferably used in the range of 0.1% by mass to 5% by mass with respect to the mass of each of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). ..

Further, as the additive, a colorant such as a pigment or a dye can be used.

As the dye, a direct dye, an acid dye, a basic dye, a reactive dye, a disperse dye and the like can be used.

As the pigment, for example, the pigments shown below can be used.

Examples of magenta pigments include C.I. I. Pigment Red 5 (azo pigment), C.I. I. Pigment Red 7 (azo pigment), C.I. I. Pigment Red 12 (azo pigment), C.I. I. Pigment Red 48 (Ca) (azo pigment), C.I. I. Pigment Red 48 (Mn) (azo pigment), C.I. I. Pigment Red 57 (Ca) (azo pigment), C.I. I. Pigment Red 57: 1 (azo pigment), C.I. I. Pigment Red 112 (azo pigment), C.I. I. Pigment Red 122 (quinacridone pigment), C.I. I. Pigment Red 123 (perylene pigment), C.I. I. Pigment Red 168 (anthraquinone pigment), C.I. I. Pigment Red 184 (azo pigment), C.I. I. Pigment Red 202 (quinacridone pigment), C.I. I. Pigment Red 209 (quinacridone pigment), C.I. I. Pigment Violet 19 (quinacridone pigment) and the like.

Examples of the cyan pigment include C.I. I. Pigment Blue 1 (lake pigment), C.I. I. Pigment Blue 15 (phthalocyanine pigment), C.I. I. Pigment Blue 15: 3 (phthalocyanine pigment), C.I. I. Pigment Blue 15: 4 (phthalocyanine pigment), C.I. I. Pigment Blue 16 (phthalocyanine pigment), C.I. I. Pigment Blue 60 (anthraquinone pigment) and the like.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1 (azo pigment), 2 (azo pigment), 3 (azo pigment), 12 (azo pigment), 13 (azo pigment), 14 (azo pigment), 16 (azo pigment), 17 (azo pigment), 73 (azo pigment), 74 (azo pigment), 75 (azo pigment), 83 (azo pigment), 93 (azo pigment), 95 (azo pigment), 97 (azo pigment), 98 (azo pigment), 109 ( Isoindolinone pigments), 110 (isoindolinone pigments), 114 (azo pigments), 120 (benzimidazolone pigments), 128 (azo pigments), 129 (azo pigments), 138 (quinophthalone pigments), 150 (azo pigments) ), 151 (benzimidazolone pigment), 154 (benzimidazolone pigment), 155 (azo pigment), 180 (benzimidazolone pigment), 185 (isoindrin pigment), 213 (quinoxaline pigment) and the like.

The black pigment is No. 1 manufactured by Mitsubishi Chemical Corporation. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B etc. are Raven 5750, 5250, 5000, 3500, 1255, 700, etc. manufactured by Colombia, Regal 400R, 330R, 660R, Mogul L, 700, Monarch 800, 880, etc. manufactured by Cabot. 900, 1000, 1100, 1300, 1400, etc. are Color Black FW1, FW2, FW2V, FW18, FW200, ColorBlack S150, S160, S170, Printex 35, manufactured by Degussa. U, V, 140U, Special Black 6, 5, 4A, 4 and the like can be mentioned.
Examples of the white pigment include titanium oxide, zinc sulfide, lead white, zinc flower, lithobon, antimony white, basic lead sulfate, basic lead silicate, barium sulfate, calcium carbonate, gypsum, silica and the like. Among these, titanium oxide is particularly preferable from the viewpoint of excellent whiteness and abrasion resistance.

In addition to the above-mentioned additives, the additives include, for example, surfactants, leveling additives such as polysiloxane, matting agents, polyester resins, polyurethane resins, vinyl resins, acrylic resins, and rubber resins. , Waxes can also be used.

The additive may be used in the range of 0.1% by mass to 5% by mass with respect to the respective masses of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). preferable.

The active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) used in the present invention include, for example, the above-mentioned monofunctional monomer, polyfunctional monomer, polymerization initiator and, if necessary, an additive. It can be manufactured by mixing.

When the pigment or the pigment and the dispersed resin are used in combination as the additive, the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) are previously prepared with the pigment and the dispersed resin. A dispersion is produced by mixing and dispersing a monofunctional monomer or a polyfunctional monomer using a disperser, and separately from the above, a monofunctional monomer, a polyfunctional monomer, a polymerization initiator and an additive are mixed as needed. The mixture can be produced by mixing the dispersion and the mixture. In the mixing and dispersing steps, heating may be performed as needed.

As the disperser, for example, a bead mill, an ultrasonic homogenizer, a high-pressure homogenizer, a paint shaker, a ball mill, a roll mill, a sand mill, a sand grinder, a dyno mill, a dispermat, an SC mill, a nanomizer, a BDM biaxial mixer and the like can be used.

The active energy ray-curable composition set (A) used in the present invention includes the combination of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) described above, and further described above. A combination of other active energy ray-curable compositions capable of forming a cured product having a composition or property different from that of the active energy ray-curable compositions (a1) and (a2) can be used.

The active energy ray-curable composition set (A) includes two or more types of active energy ray-curable composition including the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). It is preferable to select and use a composition having a static surface tension close to that at 25 ° C. in combination in order to obtain a structure having high hardness and excellent adhesion.

For example, when the active energy ray-curable composition set (A) is composed of two types, the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). Difference between the static surface tension (a1') of the active energy ray-curable composition (a1) at 25 ° C. and the static surface tension (a2') of the active energy ray-curable composition (a2) at 25 ° C. Absolute value of | static surface tension (a1')-static surface tension (a2') | is in the range of 0 mN / m to 1 mN / m for high hardness and adhesion. It is preferable to obtain an excellent structure.

The static surface tension refers to a value measured by the platinum plate method using an automatic surface tension meter manufactured by Kyowa Interface Science Co., Ltd .: DY-300.

As the active energy ray-curable composition set (A), the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) are combined with other active energy ray-curable compositions. When using the above, it is recommended to use a set of combinations in which the difference in static surface tension at 25 ° C. of all active energy ray-curable compositions is in the range of 0 mN / m to 1 mN / m. Moreover, it is preferable to obtain a structure having excellent adhesion.

Further, as the active energy ray-curable composition set (A), it is preferable to use one having a viscosity at a level that can be ejected by a jet printing method. Specifically, it is preferable to use the viscosity in the range of 3 mPa · sec to 30 mPa · sec at 25 ° C. The viscosity refers to a value measured using a rotational viscometer (viscosity measuring instrument manufactured by Toki Sangyo Co., Ltd .: TVE-20L).

Further, as the active energy ray-curable composition set (A), it is possible to use a combination of two or more active energy ray-curable compositions capable of forming cured products having different elastic modulis with high hardness. Moreover, it is preferable to obtain a structure having excellent adhesion.

For example, the storage elastic modulus (a1 ″) of the cured product of the active energy ray-curable composition (a1) at 25 ° C. and the storage elastic modulus of the cured product of the active energy ray-curable composition (a2) at 25 ° C. Elastic modulus ratio with a2 ") | Storage elastic modulus (a2") / Storage elastic modulus (a1 ") | It is better to use one in the range of 1 to 20 for high hardness and excellent adhesion. It is preferable to obtain a new structure. The elastic modulus of the cured product refers to a value measured using RSA3 manufactured by TA Instruments Japan Co., Ltd.

As the active energy ray-curable composition set (A), the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) are combined with other active energy ray-curable compositions. Can be used. In that case, the elastic modulus ratio [maximum storage elastic modulus / minimum storage elastic modulus] between the one having the maximum storage elastic modulus and the one having the minimum storage elastic modulus among all the active energy ray-curable compositions is in the range of 1 to 20. It is preferable to use a structure having high hardness and excellent adhesion.

Further, as the active energy ray-curable composition set (A), it is possible to use a combination of two or more active energy ray-curable compositions capable of forming cured products having different glass transition temperatures with high hardness. Moreover, it is preferable to obtain a structure having excellent adhesion.

Specifically, the active energy ray-curable composition set (A) includes the glass transition temperature (a1 ″) of the cured product of the active energy ray-curable composition (a1) and the active energy ray-curable composition. It is possible to use a material (a2) having a high hardness and satisfying the relationship of the glass transition temperature (a2 ") of the cured product and the glass transition temperature (a1") <glass transition temperature (a2 "). It is preferable to obtain a structure having excellent adhesion, and a cured product of the active energy ray-curable composition (a1) having a glass transition temperature (a1 ″) in the range of −50 ° C. to 100 ° C. is used. It is preferable to use a combination of the cured product of the active energy ray-curable composition (a2) having a glass transition temperature (a2 ″) in the range of 0 ° C. to 200 ° C. with high hardness and close contact. It is preferable to obtain a structure having excellent properties. The glass transition temperature of the cured product refers to a value measured using RSA3 manufactured by TA Instruments Japan Co., Ltd.

As the active energy ray-curable composition set (A), the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) are combined with other active energy ray-curable compositions. When using one, it is preferable to use a combination of at least two active energy ray-curable compositions in which the cured products have different glass transition temperatures.

As a method of applying the active energy ray-curable composition set (A), a jet printing method is adopted.

Examples of the jet printing method include a continuous type and a drop-on-demand type. As the drop-on-demand type, a piezo method, a thermal method, or the like can be used.

In the present invention, the active energy ray-curable composition set (A) can be ejected onto the surface of any substrate by the jet printing method. In the discharge step, the discharge of the active energy ray-curable composition (a1) and the discharge of the active energy ray-curable composition (a2) may be performed in parallel, and either one may be discharged. After that, the other discharge may be performed. Above all, it is preferable to perform the ejection steps in parallel in order to obtain a structure having high hardness and excellent adhesion without lowering the production efficiency.

When the active energy ray-curable composition set (A) is discharged by the jet printing method and applied to the surface of an arbitrary substrate, the active energy ray-curable composition (a1) and the active energy ray-curable composition are applied. The sex composition (a2) may be applied randomly or regularly, but may be applied randomly in order to obtain a structure having high hardness and excellent adhesion. preferable.

When applied randomly, the ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time by the jet printing method to the volume of the active energy ray-curable composition (a2). It is preferable to apply so that [volume of (a1): volume of (a2)] is in the range of 80:20 to 20:80, and is preferably applied in the range of 60:40 to 40:60. However, it is more preferable to obtain a structure having both high hardness and excellent adhesion.

The patterns for regular application include, for example, pinstripe, pencil stripe, double stripe, border, checkered pattern, gingham check, tartan check, argyle check, block check, zigzag lattice, herringbone, glen check, basket check. , Graph check, pin dot, coin dot, ring dot, bubble dot, star pattern, cross pattern and the like.

Dots (y1) made of the active energy ray-curable composition (a1) ejected by the jet printing method and landed on the surface of the base material, and dots (y2) made of the active energy ray-curable composition (a2). ) Is preferably in a shape capable of forming an elliptical shape and a circular shape, respectively, in order to obtain a structure having high hardness and good adhesion.

The application of the active energy ray-curable composition set (A) is preferably performed so that the dots of the active energy ray-curable composition contained in the set (A) are in contact with each other. The contact includes a mode in which dots are in contact with each other at their outer edges and a mode in which dots are overlapped with each other.

The coated surface of the active energy ray-curable composition set (A) is a set composed of, for example, the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) (a2). When A) is used, the dots (a2) made of the active energy ray-curable composition (a2) are contained in the matrix composed of the dots (y1) made of the active energy ray-curable composition (a1). It is preferable to form a so-called sea-island structure in which a domain composed of y2) is formed in order to obtain a structure having high hardness and good adhesion. As the structure, a structure in which a domain composed of the region (z1) is formed in a matrix composed of the region (z2) can also be preferably used in the same manner as described above.

Dots (y1) made of the active energy ray-curable composition (a1) ejected by the jet printing method and landed on the surface of the base material, and dots (y2) made of the active energy ray-curable composition (a2). ) Spreferably have a maximum diameter of 10 μm to 100 μm, and more preferably in the range of 10 μm to 60 μm in order to obtain a structure having high hardness and excellent adhesion. Further, even if the dots (y1) made of the active energy ray-curable composition (a1) and the dots (y2) made of the active energy ray-curable composition (a2) have different thicknesses, Although the thickness may be substantially the same, it is preferable that each has a thickness of 1 μm to 20 μm, and the range of 5 μm to 15 μm is high hardness and excellent adhesion. It is more preferable to obtain a structure.

Examples of the base material include paper and resin film. Examples of the resin constituting the resin film include ABS (acrylonitrile, butadiene, styrene) resin, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin, and PBT (polybutylene). ABS-based polymer alloy such as terephthalate / ABS, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic acid ester) -Examples include styrene) -based resin, PC (polycarbonate) -based resin, acrylic-based resin, methacrylic-based resin, PP (polypropylene) -based resin, and the like.

Next, a step [2] constituting the method for manufacturing the structure of the present invention will be described.

In the step [2], the active energy ray-curable composition (A) is irradiated with active energy rays on the coated surface of the active energy ray-curable composition set (A) obtained in the step [1]. This is a step of allowing a part or all of the curing reactions of a1) and the active energy ray-curable composition (a2) to proceed in parallel.

In the step [2], ultraviolet rays, electron beams, and X-rays can be used as the active energy rays, and the use of ultraviolet rays is easier to handle than X-rays and the like, and has high hardness and excellent adhesion. It is preferable to obtain a structure comprising the above.

Examples of the light source that generates the active energy ray include a mercury lamp, a metal halide lamp, a sodium lamp, a xenon lamp, a light emitting diode (LED), and a laser. Using a light emitting diode (LED) is compared with a mercury lamp or the like. It is preferable because it has high energy saving efficiency.

The integrated light intensity of the active energy rays in the entire manufacturing process of the structure is preferably, for example, in the range of integrated light intensity of 10 to 1000 mJ / cm ² , and irradiation in the range of integrated light intensity of 200 to 1000 mJ / cm ² . It is more preferable to achieve both high hardness and adhesion. The intensity of the active energy ray is preferably in the range of 100 mW / cm ² to 1000 mW / cm ² .

Further, in the step [2], a part or all of the curing reactions of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) are allowed to proceed in parallel. This is a reaction in which the curing reaction step of the active energy ray-curable composition (a1) and the curing reaction step of the active energy ray-curable composition (a2) are controlled so as to partially or completely overlap. Refers to letting.

Therefore, the step of starting the curing reaction of the active energy ray-curable composition (a2) after the curing reaction of the active energy ray-curable composition (a1) is completed and substantially stopped is described in the present invention. Is not included in the step [2] constituting the above.

The overlap between the curing reaction step of the active energy ray-curable composition (a1) and the curing reaction step of the active energy ray-curable composition (a2) is 50% or more of each curing reaction step. It is preferable to adjust it to 80% or more, more preferably to adjust it to 95% to 100%, and it is highly preferable to adjust it to 99% to 100%. It is particularly preferable to obtain a structure having excellent hardness and adhesion.

As the active energy ray-curable composition set (A), one or more other active energy ray-curable compositions together with the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). When a combination of the above is used, it is possible to carry out a part or all of the curing reaction of all the active energy ray-curable compositions in parallel to obtain a structure having high hardness and excellent adhesion. It is preferable to obtain it. In that case, the overlap of the curing reaction steps of each of the three or more types of active energy ray-curable compositions is preferably adjusted to be 50% or more of the respective curing reaction steps, and is preferably 80% or more. It is more preferable to adjust it to 95% to 100%, and it is more preferable to adjust it to 99% to 100% in order to obtain a structure having high hardness and excellent adhesion. Is particularly preferable.

Further, in the step [2], the dots (y1) made of the active energy ray-curable composition (a1) ejected from the ejection nozzle (x1) by the jet printing method and landed on the surface of the substrate, and the ejection nozzle. It is preferable to cure the active energy ray-curable composition (a2) in contact with the dots (y2) discharged from (x2) and landed on the surface of the substrate in order to obtain an excellent structure. .. The contact refers to a mode in which the outer edges of the dots (y1), the dots (y1) and the dots (y2), and the dots (y2) are in contact with each other, or the dots are overlapped with each other. include.

On the coated surface after irradiation with the active energy rays, a chemical bond is formed between the cured product of the dots (y1) and the cured product of the dots (y2), which results in high hardness and adhesion. It is preferable to obtain an excellent structure. Examples of the chemical bond include a carbon-carbon covalent bond. The chemical bond is preferably formed between the dots (y1), between the dots (y1) and (y2), and between the dots (y2). As the active energy ray-curable composition set (A), one or more other active energy ray-curable compositions together with the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). When a combination of the above is used, it is preferable that the dots (y1), the dots (y2), and the other dots are cured in a state where a chemical bond is formed as described above.

The structure of the present invention produced by going through at least the steps [1] and [2] is a region formed by a cured product of dots (y1) made of the active energy ray-curable composition (a1). It has (z1) and a region (z2) formed by a cured product of dots (y2) made of the active energy ray-curable composition (a2).

As the structure, a structure in which the ratio of the region (z1) and the region (z2) [area of region (z1): area of region (z2)] is in the range of 80:20 to 20:80 is used. It is preferable to use a structure in the range of 60:40 to 40:60 in order to obtain a structure having both high hardness and excellent adhesion.

Further, as the structure, depending on the region (z1) and the region (z2), a pin stripe, a pencil stripe, a double stripe, a border, a checkered pattern, a gingham check, a tartan check, an argyle check, a block check, and a staggered lattice. , Herringbone, Glen check, Basket check, Graph check, Pin dot, Coin dot, Ring dot, Bubble dot, Star pattern, Cross pattern, etc. can be used. Further, as the structure, a structure having a random pattern depending on the region (z1) and the region (z2) can be used.

As the structure, for example, when a set (A) composed of two types of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) is used, the said. It is preferable to use a matrix having a so-called sea-island structure in which a domain consisting of the region (z2) is formed in a matrix composed of the region (z1) in order to obtain high hardness and good adhesion. As the structure, a structure in which a domain composed of the region (z1) is formed in a matrix composed of the region (z2) can also be preferably used in the same manner as described above.

As the structure, those having different thicknesses of the region (z1) and the region (z2) and those having substantially the same thickness can be used, each having a thickness of 1 μm to 20 μm. It is preferable that the structure has a strength, and it is more preferable that the structure has a hardness in the range of 5 μm to 15 μm in order to obtain a structure having high hardness and excellent adhesion.

In the structure, the size (maximum diameter) of the cured product of the dots (y1) constituting the region (z1) and the cured product of the dots (y2) constituting the region (z2) is 10 μm or more, respectively. It is preferably those having a maximum diameter of 100 μm, and more preferably in the range of 10 μm to 60 μm in order to obtain a structure having high hardness and excellent adhesion.

The structure obtained by the above method can be used for products and parts thereof that require a foldable level of flexibility, such as a flexible display. Examples of the structure include a three-dimensional object such as synthetic leather, a cured coating film such as a hard coat layer, and a laminate of the cured coating film and a base material.

Hereinafter, the present invention will be described in more detail by way of examples.

[Preparation example of pigment dispersion liquid]
Preparation Example of Magenta Pigment Dispersion Liquid (1) 10 parts by mass of Fastgen Super Magenta RTS (Magenta Pigment CI Pigment Red 122 manufactured by DIC Corporation), 5 parts by mass of Sol Spurs 32000 (manufactured by Lubrizol), and simply. A magenta pigment dispersion (1) was obtained by mixing 85 parts by mass of a functional monomer (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) with a stirrer for 1 hour and then treating with a bead mill for 2 hours.

Preparation Example of Cyan Pigment Dispersion Liquid (2) Fastgen Blue TGR-G (Phythalocyanine Pigment CI Pigment Blue 15: 4 manufactured by DIC Corporation) 10 parts by mass and M-222 (manufactured by MIWON) as a polyfunctional monomer 87 parts by mass of dipropylene glycol diacrylate) and 3 parts by mass of Sol Spurs 32000 (manufactured by Lubrizol) were stirred and mixed with a stirrer for 1 hour, and then treated with a bead mill for 2 hours to obtain a cyan pigment dispersion (2). Obtained.

[Preparation Example of Active Energy Ray Curable Composition (a1)]
40 parts by mass of the magenta pigment dispersion (1), 6 parts by mass of M-3130 (ethylene oxide-modified trimethylol propanetriacrylate manufactured by MIWON) as a polyfunctional monomer, and M-240 (ethylene oxide-modified bisphenol A manufactured by MIWON). 5 parts by mass of diacrylate), 10 parts by mass of IBXA (isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 12 parts by mass of V-CAP (N-vinyl caprolactam manufactured by ISP), and POA as monofunctional monomers. 20 parts by mass of (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.), 0.2 parts by mass of KF-54 (polysiloxane manufactured by Shinetsu Chemical Industry Co., Ltd.) as an additive, and Irg. 819 (BASF bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) by mass and Irg. 5 parts by mass of TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF), 1 part by mass of DETX-S (diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.), and methquinone (Seiko) as a polymerization inhibitor. Dibutylhydroquinone manufactured by Kagaku Co., Ltd.) was mixed with 0.1 parts by mass, and the Irg. 819 and Irg. The active energy ray-curable composition (a1) was obtained by stirring at 60 ° C. for 30 minutes or more until TPO, DETX-S and methquinone were dissolved.

The active energy ray-curable composition (a1) contained 87% by mass of a monofunctional monomer and 13% by mass of a polyfunctional monomer with respect to the total amount of the polymerizable compound. The static surface tension of the active energy ray-curable composition (a1) at 25 ° C. was measured by the platinum plate method using an automatic surface tensiometer manufactured by Kyowa Interface Science Co., Ltd .: DY-300, and was 28.8 mN / m. Met.

[Preparation Example of Active Energy Ray Curable Composition (a2)]
10 parts by mass of the cyan pigment dispersion liquid (2), 4 parts by mass of Unidic V-5500 (epoxyacrylate manufactured by DIC Co., Ltd.) as a polyfunctional monomer, and M-3130 (ethylene oxide-modified trimethylolpropanetri manufactured by MIWON Co., Ltd.). 24 parts by mass of acrylate), 42 parts by mass of M-200 (hexanediol diacrylate manufactured by MIWON), 8 parts by mass of POA (phenoxyethyl acrylate manufactured by Kyoeisha Chemical Co., Ltd.) as a monofunctional monomer, and KF as an additive. -54 (Polysiloxane manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.2 parts by mass, Irg. 819 (BASF bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) by mass and Irg. 6 parts by mass of TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by BASF), 2 parts by mass of DETX-S (diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd.), and methquinone (Seiko) as a polymerization inhibitor. Dibutylhydroquinone manufactured by Kagaku Co., Ltd.) was mixed with 0.1 parts by mass, and the Irg. 819 and Irg. The active energy ray-curable composition (a2) was obtained by stirring at 60 ° C. for 30 minutes or more until TPO, DETX-S and methquinone were dissolved.

The active energy ray-curable composition (a2) contained 9% by mass of a monofunctional monomer and 91% by mass of a polyfunctional monomer with respect to the total amount of the polymerizable compound.

The static surface tension of the active energy ray-curable composition (a2) at 25 ° C. was measured by the platinum plate method using an automatic surface tension meter manufactured by Kyowa Interface Science Co., Ltd .: DY-300, and was 28.9 mN /. It was m.

[Example 1]
An ejection evaluation device equipped with an inkjet head capable of ejecting two or more types of ink and an LED-UV irradiation device (λmax = 385 nm) was prepared.

Next, the ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time to the volume of the active energy ray-curable composition (a2) was set to 80:20.

Next, the active energy ray-curable compositions (a1) and (a2) were randomly and simultaneously ejected onto a vinyl chloride substrate (Hishi plate manufactured by Mitsubishi Plastics Co., Ltd.).

Immediately after the ejection, the surface of the vinyl chloride substrate is exposed to dots having a diameter of about 50 μm by irradiating the ejection surface with ultraviolet rays using the LED-UV irradiation device so that the integrated light amount becomes 240 mJ / cm ² . A structure in which a cured coating film having a length of 5 cm × width of 5 cm and a thickness of about 6 μm was laminated was obtained.

The overlap between the curing reaction step of the active energy ray-curable composition (a1) and the curing reaction step of the active energy ray-curable composition (a2) is 99% to 100% of each curing reaction step. Adjusted to. Also in Examples 2 to 5, the overlap between the curing reaction step of the active energy ray-curable composition (a1) and the curing reaction step of the active energy ray-curable composition (a2) is the same as in Example 1. It was adjusted to be 99% to 100% of each curing reaction step.

When the cured coating film constituting the structure was observed using a digital microscope VHX-600 manufactured by Keyence Co., Ltd. at a magnification of 500 times, the active energy ray curable composition existing per area shown in FIG. 1 was observed. The ratio of the region (z1) formed by the cured product of the dots made of the substance (a1) to the region (z2) formed by the cured product of the dots made of the active energy ray-curable composition (a2). The area of (z1): the area of the area (z2)] was 80:20. Further, the structure had a sea-island structure in which the matrix composed of the region (z2) was randomly present in the matrix composed of the region (z1).

[Example 2]
The ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time to the volume of the active energy ray-curable composition (a2) was changed from 80:20 to 60:40. Except for this, a structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the vinyl chloride substrate was obtained by the same method as in Example 1.

When the cured coating film constituting the structure was observed using a digital microscope VHX-600 manufactured by Keyence Co., Ltd. at a magnification of 500 times, the active energy ray-curable composition present in the same area as in FIG. The ratio of the region (z1) formed by the cured product of the dots composed of (a1) to the region (z2) formed by the cured product of the dots composed of the active energy ray-curable composition (a2) [region (z2). The area of z1): the area of the area (z2)] was 60:40. Further, the structure had a sea-island structure in which the matrix composed of the region (z2) was randomly present in the matrix composed of the region (z1).

[Example 3]
The ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time to the volume of the active energy ray-curable composition (a2) was changed from 80:20 to 50:50. Except for this, a structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the vinyl chloride substrate was obtained by the same method as in Example 1.

When the cured coating film constituting the structure was observed using a digital microscope VHX-600 manufactured by Keyence Co., Ltd. at a magnification of 500 times, the active energy ray-curable composition present in the same area as in FIG. The ratio of the region (z1) formed by the cured product of the dots composed of (a1) to the region (z2) formed by the cured product of the dots composed of the active energy ray-curable composition (a2) [region (z2). The area of z1): the area of the area (z2)] was 50:50.

[Example 4]
The ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time to the volume of the active energy ray-curable composition (a2) was changed from 80:20 to 40:60. Except for this, a structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the vinyl chloride substrate was obtained by the same method as in Example 1.

When the cured coating film constituting the structure was observed using a digital microscope VHX-600 manufactured by Keyence Co., Ltd. at a magnification of 500 times, the active energy ray-curable composition present in the same area as in FIG. The ratio of the region (z1) formed by the cured product of the dots composed of (a1) to the region (z2) formed by the cured product of the dots composed of the active energy ray-curable composition (a2) [region (z2). The area of z1): the area of the area (z2)] was 40:60. Further, the structure had a sea-island structure in which the matrix composed of the region (z1) was randomly present in the matrix composed of the region (z2).

[Example 5]
The ratio of the volume of the active energy ray-curable composition (a1) discharged per unit time to the volume of the active energy ray-curable composition (a2) was changed from 80:20 to 20:80. Except for this, a structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the vinyl chloride substrate was obtained by the same method as in Example 1.

When the cured coating film constituting the structure was observed using a digital microscope VHX-600 manufactured by Keyence Co., Ltd. at a magnification of 500 times, the active energy ray curable property existing in the same area as in FIG. 1 was observed. The ratio of the region (z1) formed by the cured product of the dots made of the composition (a1) to the region (z2) formed by the cured product of the dots made of the active energy ray-curable composition (a2) [ The area of the region (z1): the area of the region (z2)] was 20:80. Further, the structure had a sea-island structure in which the matrix composed of the region (z1) was randomly present in the matrix composed of the region (z2).

[Comparative Example 1]
A mixture was obtained by mixing and stirring 80 parts by mass of the active energy ray-curable composition (a1) and 20 parts by mass of the active energy ray-curable composition (a2).

Next, the mixture was applied to the surface of a vinyl chloride substrate (Mitsubishi Plastics Co., Ltd. Hishi Plate) using a spin coater.

By irradiating the coated surface with an LED irradiation device (λmax = 385 nm) manufactured by Hamamatsu Photonics Co., Ltd. equipped with a stage moving device, an amount of integrated light of 240 mJ / cm ² is applied to the surface of the vinyl chloride substrate. A structure in which a cured coating film having a length of 5 cm × width of 5 cm and a thickness of about 6 μm was laminated was obtained.

When the cured coating film was observed with a digital microscope VHX-600 manufactured by KEYENCE CORPORATION, a sea-island structure composed of the cured products of the active energy ray-curable compositions (a1) and (a2) was not formed ( Figure 2). Further, it is formed by a region (z1) formed by a cured product of dots made of the active energy ray-curable composition (a1) and a cured product of dots made of the active energy ray-curable composition (a2). The ratio to the region (z2) [area of region (z1): area of region (z2)] could not be measured either. Hereinafter, the structures obtained in Comparative Examples 2 to 10 did not have a sea-island structure, and the ratio [area of region (z1): area of region (z2)] could not be measured.

[Comparative Example 2]
On the surface of the vinyl chloride substrate by the same method as in Comparative Example 1 except that the mass ratio of the mixture containing the active energy ray-curable compositions (a1) and (a2) was changed from 80:20 to 60:40. A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 3]
On the surface of the vinyl chloride substrate by the same method as in Comparative Example 1 except that the mass ratio of the mixture containing the active energy ray-curable compositions (a1) and (a2) was changed from 80:20 to 50:50. A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 4]
On the surface of the vinyl chloride substrate by the same method as in Comparative Example 1 except that the mass ratio of the mixture containing the active energy ray-curable compositions (a1) and (a2) was changed from 80:20 to 40:60. A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 5]
On the surface of the vinyl chloride substrate by the same method as in Comparative Example 1 except that the mass ratio of the mixture containing the active energy ray-curable compositions (a1) and (a2) was changed from 80:20 to 20:80. A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 6]
On the surface of the vinyl chloride substrate by the same method as in Example 1 except that only the active energy ray-curable composition (a1) was used instead of the active energy ray-curable compositions (a1) and (a2). A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 7]
On the surface of the vinyl chloride substrate by the same method as in Example 1 except that only the active energy ray-curable composition (a2) was used instead of the active energy ray-curable compositions (a1) and (a2). A structure in which a cured coating film having a thickness of about 6 μm was laminated was obtained.

[Comparative Example 8]
Only a mixture containing 50 parts by mass of the active energy ray-curable composition (a1) and 50 parts by mass of the active energy ray-curable composition (a2) instead of the active energy ray-curable compositions (a1) and (a2). A structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of a vinyl chloride substrate was obtained by the same method as in Example 1 except that the above was used.

[Comparative Example 9]
Vinyl chloride in the same manner as in Comparative Example 1 except that only the active energy ray-curable composition (a1) was used instead of the mixture containing the active energy ray-curable compositions (a1) and (a2). A structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the substrate was obtained.

[Comparative Example 10]
Vinyl chloride in the same manner as in Comparative Example 1 except that only the active energy ray-curable composition (a2) was used instead of the mixture containing the active energy ray-curable compositions (a1) and (a2). A structure in which a cured coating film having a thickness of about 6 μm was laminated on the surface of the substrate was obtained.

[Measurement method of elastic modulus and glass transition temperature (Tg)]
The active energy ray-curable compositions (a1) and (a2) were applied to the surface of a glass substrate (manufactured by Toshin Riko Co., Ltd.) by a spin coating method.

By irradiating the coated surface with an LED irradiation device (λmax = 385 nm) manufactured by Hamamatsu Photonics Co., Ltd. equipped with a stage moving device, an amount of integrated light of 240 mJ / cm ² is applied to the surface of the glass substrate vertically. A structure in which a cured coating film having a thickness of 10 cm × width of 10 cm and a thickness of about 6 μm was laminated was obtained.

Next, by repeating the steps of applying and curing the active energy ray-curable compositions (a1) and (a2) on the surface of the cured coating film by the method described above, a cured coating film having a thickness of 50 μm is formed. A structure having was obtained.

Next, a cured coating film having a thickness of 50 μm was peeled off from the glass substrate constituting the structure and cut into a width of 6 mm with a dumbbell cutter to obtain a test piece.

Next, the dynamic viscoelasticity (DMA) of the test piece was subjected to RSA3 manufactured by TA Instruments Japan Co., Ltd. (distance between chucks: 20 mm, measurement temperature range 10 ° C. to 90 ° C., temperature rise rate: 3 ° C.). Using / min, frequency: 3.5 Hz), the storage elastic modulus at 25 ° C. and the glass transition temperature (Tg) obtained from the peak top of tan δ (loss elastic modulus / storage elastic modulus) were measured.

As a result, the storage elastic modulus (a1 ") of the cured product of the active energy ray-curable composition (a1) was 0.4 GPa and the glass transition temperature was 45 ° C., and the active energy ray-curable composition. The storage elastic modulus (a2 ") of the cured product of (a2) was 0.7 GPa, and the glass transition temperature was 80 ° C.

The storage elastic modulus (a1 ") of the cured product of the active energy ray-curable composition (a1) at 25 ° C. and the storage elastic modulus (a2" of the cured product of the active energy ray-curable composition (a2) at 25 ° C. ) And the elastic modulus ratio | storage elastic modulus (a2 ") / storage elastic modulus (a1") | was 1.75.

[hardness]
The hardness of the surface of the cured coating film constituting the structures obtained in Examples and Comparative Examples was evaluated by a hand-painting method according to JIS-K5600-5-4.

The surface hardness of the cured coating film constituting the structures obtained in Examples and Comparative Examples was evaluated by the following method.

A pencil with a sharp tip was created by sharpening a pencil of any hardness with a pencil sharpener. Next, the pencil was cut so that the diameter of the tip (core) of the pencil became a flat surface having the same size as the diameter of the core before cutting.

Place the pencil on the surface of the cured coating film at 45 ° to the surface, scratch 1 cm at a speed of about 1 cm / sec with a load of about 1 kg, and visually check for tearing of the cured coating film. Evaluated in. The highest hardness among the pencil hardnesses in which the cured coating film was not torn is shown in the table.

[Adhesion]
Using a cutter knife, cuts consisting of 5 vertical and 5 horizontal squares and 2 mm wide squares (25 squares) were made on the surface of the cured coating film constituting the structures obtained in Examples and Comparative Examples. .. Next, a cellophane adhesive tape manufactured by Nichiban Co., Ltd. was attached to the surface of the squares and rubbed with a nail 10 times.

Next, after peeling at a peeling speed of about 1 cm / sec, the surface of the cured coating film was visually observed, and the number of cured coating films remaining without peeling from the vinyl chloride substrate was counted.

In Tables 1 and 2, "J" indicates a jet printing method, and "SC" indicates a spin coating method.

Claims (4)

A step of ejecting an active energy ray-curable composition set (A) composed of at least two types of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) by a jet printing method [ 1], and by irradiating the discharged region with active energy rays, a part of each curing reaction of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2) or It has a step [2] of obtaining a structure by advancing all of them in parallel.
The active energy ray-curable composition (a1) reacts with the total amount of the polymerizable compound (A) contained in the active energy ray-curable composition (a1) by irradiating the active energy rays. The active energy ray-curable composition (a2) is contained in the active energy ray-curable composition (a2) and contains 60% by mass or more of a monofunctional monomer having one functional group to be obtained. It contains 60% by mass or more of a polyfunctional monomer having two or more functional groups capable of reacting with the total amount of the polymerizable compound (A) by being irradiated with active energy rays.
The storage elastic modulus (a1 ") of the cured product of the active energy ray-curable composition (a1) at 25 ° C. and the storage elastic modulus (a2" of the cured product of the active energy ray-curable composition (a2) at 25 ° C. ) And the elastic modulus ratio | storage elastic modulus (a2 ") / storage elastic modulus (a1") | is in the range of 1 to 20.
Difference between the static surface tension (a1') of the active energy ray-curable composition (a1) at 25 ° C. and the static surface tension (a2') of the active energy ray-curable composition (a2) at 25 ° C. Absolute value | Static surface tension (a1')-Static surface tension (a2') | A method for manufacturing a structure, characterized in that the range is 0 mN / m to 1 mN / m . The dots (y1) made of the active energy ray-curable composition (a1) ejected from the ejection nozzle (x1) by the jet printing method and landed on the surface of the substrate, and the substrate ejected from the ejection nozzle (x2). The method for producing a structure according to claim 1, wherein the dots (y2) made of the active energy ray-curable composition (a2) landed on the surface are cured in contact with each other. The structure is composed of dots in a matrix formed by a cured product of dots composed of one of the active energy ray-curable composition (a1) and the active energy ray-curable composition (a2). The method for producing a structure according to claim 1 or 2, which has a sea-island structure in which a domain formed by the cured product of No. 1 is present. The method for manufacturing a structure according to any one of claims 1 to 3 , wherein the integrated light amount of the active energy rays in the entire manufacturing process of the structure is 10 mJ / cm ² to 1000 mJ / cm ² .

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