JP7247362B2 - Thermosetting resin composition, coating material for printing, cured product, laminate, and method for producing laminate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosetting resin composition, a coating material for printing, a cured product, a laminate, and a method for producing a laminate.

OPP (biaxially oriented polypropylene film), which is used as a base material for stickers and labels, has low surface free energy and, for example, a water contact angle of 100° or more. Therefore, usually, the printability of ink is improved by forming an easy-printing layer on OPP, but this easy-printing layer does not have sufficient scratch resistance, and the easy-printing layer is scratched when handled. There is a problem that the design is likely to be damaged.

Further, in Patent Document 1, as a release coating agent capable of forming a cured film having excellent coating film appearance and excellent release performance and solvent resistance, a melamine resin (A) and a C 12-24 fat Disclosed is a thermosetting release coating comprising a self-condensate of a group hydroxycarboxylic acid (B), and an acid catalyst (C), which may further comprise a polyol (D), such as a polyolefin polyol. It is

Further, Patent Document 2 discloses a coating liquid containing a hexamethylolmelamine prepolymer as a coating liquid for forming an easily printable layer (see Examples of Patent Document 2). In Cited Document 2, a coating liquid is applied to the surface of a resin base material, the coating liquid is heat-treated to form a melamine resin layer, and then an image is printed on the melamine resin layer using a water-based ink. there is

JP 2019-94483 A JP 2019-64238 A

However, Patent Document 1 does not include any examples of combining melamine resins and polyolefin polyols, nor does it describe any special effects of combining melamine resins and polyolefin polyols. In addition, when the present inventors conducted tests using the methylated melamine resin used in Examples of Patent Document 1 and an olefin polymer, the obtained cured film had low transparency and could not be used in practice. There was found.

Further, in Patent Document 2, a melamine resin layer is formed as an easy-to-print layer on the surface of a resin base material, but the adhesion of the melamine resin layer to the resin base material is insufficient.

An object of the present invention is to provide a thermosetting resin composition, a coating material for printing, a cured product, a laminate, and a method for producing a laminate that can form a cured film having excellent adhesion.

As a result of intensive studies by the present inventors, a thermosetting resin composition containing an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less, a radical polymer having a hydroxyl group, and an acid catalyst We have found that the above problems can be solved by using a substance.

That is, the present invention includes the following aspects.

The present invention [1] comprises (A) an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less, (B) a radical polymer having a hydroxyl group, and (C) an acid catalyst. Including the containing thermosetting resin composition.

The present invention [2] includes the thermosetting resin composition according to [1] above, wherein the mass ratio of the alkyl etherified amino resin to the radical polymer is in the range of 50/50 to 99/1. .

The present invention [3] includes the thermosetting resin composition according to [1] above, wherein the mass ratio of the alkyl etherified amino resin to the radical polymer is in the range of 1/99 to 49/51. .

The present invention [4] includes the thermosetting resin composition according to any one of the above [1] to [3], wherein the alkyl-etherified amino resin is a butyl-etherified melamine resin.

The present invention [5] includes the thermosetting resin composition according to any one of [1] to [4] above, wherein the radical polymer has a hydroxyl value of 20 to 200 mgKOH/g.

The present invention [6] is the thermosetting according to any one of the above [1] to [5], wherein the radical polymer has a solubility parameter δ (SP value) of 8.0 to 9.0. containing a flexible resin composition.

In the present invention [7], the radical polymer is a reaction product of a hydroxyl-free radical polymer and a hydroxyl-containing monomer, and the hydroxyl-free radical polymer has 2 to 20 carbon atoms. [1] above, which is at least one polymer selected from the group consisting of an olefin polymer, an olefin polymer having a plurality of double bonds, and a copolymer of an olefin and another radically polymerizable monomer. The thermosetting resin composition according to any one of [6] is included.

The present invention [8] includes the thermosetting resin composition according to any one of [1] to [7] above, wherein the acid catalyst is p-toluenesulfonic acid.

The present invention [9] further comprises (D) a surface conditioner containing fluorine in an amount of 0.1 to 30 parts by mass based on 100 parts by mass of the total of the alkyl etherified amino resin and the radical polymer. The thermosetting resin composition according to any one of [1] to [8] above is included.

The present invention [10] includes a printing coating material comprising the thermosetting resin composition according to any one of [1] to [9] above.

The present invention [11] includes a cured product comprising the thermosetting resin composition according to any one of [1] to [9] above.

The present invention [12] includes the cured product of [11] above, which has a water contact angle of 20 to 89°.

The present invention [13] is a laminate in which a substrate, a cured film and a printed layer are laminated in this order, wherein the cured film contains the cured product according to [11] above.

The present invention [14] includes the laminate according to the above [13], wherein the substrate comprises an olefin polymer.

The present invention [15] includes the laminate according to [13] or [14] above, wherein the substrate includes a label including an adhesive area and a non-adhesive area.

The present invention [16] is a method of applying the thermosetting resin composition according to any one of the above [1] to [9] to a substrate, followed by applying the thermosetting resin composition to 60 to 160 C. to form a cured film.

The thermosetting resin composition of the present invention contains an alkyl etherified amino resin having an SP value of 10.0 or less, a radical polymer having a hydroxyl group, and an acid catalyst. can be formed.

Since the coating material for printing of the present invention contains the thermosetting resin composition described above, it can form a cured film having excellent adhesion.

Since the cured product of the present invention is composed of the thermosetting resin composition described above, it has excellent adhesion.

Since the laminate of the present invention includes a cured film containing the above-described cured product, it is possible to improve the adhesion of the cured film to the substrate.

The label of the present invention includes the laminate described above, and the substrate includes an adhesive region and a non-adhesive region. Therefore, the label can be attached to an object while improving the adhesion of the cured film to the substrate. can be done.

The laminate production method of the present invention can smoothly produce the laminate described above.

FIG. 1 is a side sectional view of a product label as one embodiment of the label of the present invention. FIG. 2A is a bottom view of one embodiment of the product label shown in FIG. 1 (with the adhesive area located in the center). FIG. 2B is a bottom view of another embodiment of the product label shown in FIG.

The thermosetting resin composition of the present invention (hereinafter also simply referred to as "the composition of the present invention") comprises (A) an alkyl etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less; It contains (B) a radical polymer having a hydroxyl group and (C) an acid catalyst. Details of each component are shown below.

<Alkyl etherified amino resin (A)>
The alkyl-etherified amino resin (A) used in the present invention (hereinafter also simply referred to as "amino resin (A)") is an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less. be. Alkyl-etherified amino resin is an amino resin (the amino resin refers to a thermosetting resin obtained from an amino compound and formaldehyde.) At least part of the methylol group is alkyl-etherified (e.g., methyl ether , ethyl-etherified, propyl-etherified, n-butyl-etherified, iso-butyl-etherified, etc.).

The SP value is generally called a solubility parameter among those skilled in the art, and is a measure of the degree of hydrophilicity or hydrophobicity of a resin. It is an important measure. The solubility parameter can be numerically quantified, for example, based on turbidimetry (references: KW Suh, DH Clarke J. Polymer. Sci., A-1, 5, 1671 (1967).). A solubility parameter herein is a parameter determined by a turbidimetric method. The solubility parameter by the turbidity measurement method is obtained, for example, by dissolving the resin solid content (predetermined mass) to be measured in a certain amount of a good solvent (such as acetone), and then adding water or a poor solvent such as hexane dropwise. can be obtained from each titration amount until the resin is insolubilized and turbidity is generated in the solution by the known calculation method described in the above-mentioned reference.

The SP value of the amino resin (A) is 10.0 or less, preferably 9.0 to 9.8, more preferably 9.1 to 9.5. When the SP value of the amino resin (A) is within the above range, the compatibility with the radical polymer (B) described later becomes good, and the appearance, adhesion to polyolefin substrates, scratch resistance and printability are improved. An excellent coating film (cured film) can be obtained.

Preferred examples of the amino resin (A) include butyl-etherified melamine resins, and particularly preferred are full-alkyl butyl-etherified melamine resins, because of their excellent compatibility with the radical polymer (B) having a hydroxyl group.

The amino resin (A) can be used alone or in combination of two or more.

As a commercially available product of the amino resin (A), butyl etherified melamine resins such as “Uban 20SB” and “Uban 520” manufactured by Mitsui Chemicals, Inc. can be used.

The amino resin (A) preferably has a polystyrene equivalent weight average molecular weight measured by GPC (gel permeation chromatography) of 1,000 to 8,000, more preferably 1,200 to 7,000. 000, more preferably 1,500 to 6,000. The weight-average molecular weight can be measured according to the method described in Examples below (the same applies hereinafter). When the weight average molecular weight of the amino resin (A) is within the above range, it is possible to obtain a resin composition having an appropriate viscosity, and to obtain a cured product excellent in compatibility, mechanical properties, smoothness, appearance, etc. can.

The amino resin (A) is preferably obtained by condensing melamine, formaldehyde and an alcohol having an alkyl chain of 1 to 6 carbon atoms in the presence of an acid catalyst. As the alcohol, for example, methanol, ethanol, propanol, n-butanol, iso-butanol, etc. are used. As the alcohol, a hydrous alcohol may be used, or an alcohol other than the main alcohol may be used. A so-called mixed alcohol containing a small amount may also be used.

The melamine is not particularly limited, and may be synthesized by a conventionally known method, or may be a commercially available product. The formaldehyde may be an aqueous solution or solid paraformaldehyde. Paraformaldehyde having a formalin concentration of 80% by mass or more is preferable from the viewpoint of economy.

The solid content mass ratio of the amino resin (A) to the radical polymer (B) described later (amino resin (A)/radical polymer (B)) is, for example, 1/99 to 99/1, preferably 10/ 90 to 95/5. When the content of the amino resin (A) is within the above range, it is possible to reliably improve the adhesiveness of the cured film to the substrate.

Further, the solid content mass ratio of the amino resin (A) to the radical polymer (B) is preferably 50/50 to 99/1, more preferably 60/40 to 99/1, from the viewpoint of scratch resistance. More preferably 60/40 to 95/5, particularly preferably 65/35 to 90/10. When the solid content mass ratio of the amino resin (A) to the radical polymer (B) is within the above range, a coating film (cured film) having an excellent balance between coating film appearance, adhesion and scratch resistance can be obtained. In particular, when the solid content mass ratio of the amino resin (A) to the radical polymer (B) is 65/35 or more, the scratch resistance of the cured film can be improved. Further, when the solid content mass ratio of the amino resin (A) to the radical polymer (B) is 90/10 or less, the adhesion of the cured film can be improved.

Further, the solid content mass ratio of the amino resin (A) to the radical polymer (B) is preferably 1/99 to 49/51, more preferably 10/90 to 40/60 from the viewpoint of printability. . When the solid content mass ratio of the amino resin (A) to the radical polymer (B) is within the above range, it is possible to reliably impart excellent printability to the ink to the cured film.

Further, the solid content mass ratio of the amino resin (A) to the radical polymer (B) is preferably 20/80 to 70/30, more preferably 20/30, from the viewpoint of the balance between scratch resistance and printability. 80 to 60/40.

<Radical polymer having a hydroxyl group)>
The radical polymer (B) having a hydroxyl group (hereinafter also simply referred to as "radical polymer (B))") used in the present invention is a radical polymer having no hydroxyl group modified with a monomer having a hydroxyl group. obtained by In other words, the hydroxyl-containing radical polymer (B) is a reaction product between a hydroxyl-free radical polymer and a hydroxyl-containing monomer. In the following description, the pre-modified radical polymer having no hydroxyl group is referred to as the pre-modified radical polymer and distinguished from the hydroxyl-containing radical polymer (B).

The radical polymer before modification is a polymer of radical polymerizable monomers, preferably a polymer of radical polymerizable monomers containing at least an olefin (olefin-based polymer). Olefins are one example of radically polymerizable monomers.

Examples of pre-modified radical polymers (olefin-based polymers) include polymers of olefins having 2 to 20 carbon atoms, polymers of olefins having multiple double bonds, and copolymers of olefins and other radically polymerizable monomers. is mentioned. In other words, radical polymers having no hydroxyl groups are, for example, polymers of olefins having 2 to 20 carbon atoms, polymers of olefins having a plurality of double bonds, and copolymerization of olefins with other radically polymerizable monomers. It is at least one olefinic polymer selected from the group consisting of coalescence.

Polymers of olefins having 2 to 20 carbon atoms specifically contain structural units derived from α-olefins having 4 to 20 carbon atoms. That is, the polymer of an olefin having 2 to 20 carbon atoms is a homopolymer composed of an α-olefin having 4 to 20 carbon atoms, or an α-olefin having 4 to 20 carbon atoms and an olefin having 2 to 3 carbon atoms. It is a copolymer.

Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Linear or branched α-olefins such as 1-hexadecene, 1-octadecene and 1-eicosene are included.

The α-olefin having 4 to 20 carbon atoms is preferably a linear olefin having 4 to 10 carbon atoms, more preferably a linear olefin having 4 to 6 carbon atoms, and still more preferably 1-butene. is mentioned. By using 1-butene as the α-olefin having 4 to 20 carbon atoms, both good solvent solubility and excellent resin strength can be achieved. These can be used alone or in combination of two or more.

Examples of olefins having 2 to 3 carbon atoms include ethylene and propylene, preferably propylene.

The olefins having 2 to 20 carbon atoms include, for example, the above olefins having 2 to 3 carbon atoms and the α-olefins having 4 to 20 carbon atoms. These can be used alone or in combination of two or more. The olefins having 2 to 20 carbon atoms preferably include ethylene, propylene and 1-butene, more preferably a combination of propylene and 1-butene.

Specifically, the olefin polymer having multiple double bonds contains structural units derived from an olefin having multiple double bonds.

Examples of olefins having multiple double bonds include diolefins, triolefins, and tetraolefins. Specific examples of olefins having multiple double bonds include 1,2-butadiene, 1,3-butadiene, 3-methyl-1,2-butadiene, 2-methyl-1,3-butadiene, 1,5- hexadiene and the like. 1,3-butadiene is preferably used from the viewpoint of excellent compatibility with the amino resin (A) and the dilution solvent described later.

Copolymers of olefins and other radically polymerizable monomers specifically contain structural units derived from the aforementioned olefins and structural units derived from radically polymerizable monomers other than olefins.

Examples of radically polymerizable monomers other than olefins include styrene and acrylonitrile.

The radical polymer before modification can be used alone or in combination of two or more.

Among the pre-modified radical polymers, preferred are copolymers of olefins and other radically polymerizable monomers, and more preferred are copolymers of olefins having 2 to 20 carbon atoms and styrene. and more preferably a copolymer of an olefin having 2 to 6 carbon atoms and styrene.

Especially preferred copolymers of olefins having 2 to 6 carbon atoms and styrene include styrene/ethylene/1-butene/styrene copolymers and styrene/ethylene/propylene/styrene copolymers.

A monomer having a hydroxyl group undergoes an addition reaction with the main chain of the pre-modified radical polymer. As a result, hydroxyl groups are introduced into the pre-modified radical polymer to prepare a hydroxyl-containing radical polymer (B).

A monomer having a hydroxyl group has an ethylenically unsaturated double bond in addition to the hydroxyl group. Examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates. In addition, methacrylate and acrylate are mentioned as (meth)acrylate.

Examples of hydroxyalkyl (meth)acrylates include hydroxyalkyl (meth)acrylates having a hydroxyalkyl group having 2 to 4 carbon atoms, specifically 2-hydroxyethyl (meth)acrylate, 3-hydroxy Examples include propyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate, preferably hydroxypropyl (meth)acrylate.

Hydroxyalkyl (meth)acrylates can be used alone or in combination of two or more.

As the hydroxyl group-containing radical polymer (B), particularly preferred are 2-hydroxypropyl acrylate-modified styrene/ethylene/1-butene/styrene copolymers and 2-hydroxypropyl acrylate-modified styrene/ethylene/propylene/styrene copolymers. polymers.

The hydroxyl value of the radical polymer (B) is, for example, 10 to 250 mgKOH/g, preferably 20 to 200 mgKOH/g, more preferably 25 to 200 mgKOH/g, still more preferably 30 to 150 mgKOH/g. . The hydroxyl value can be measured according to the method described in Examples below. When the hydroxyl value is within the above range, the compatibility with the amino resin (A) is good, a transparent coating film (cured film) is obtained, and the scratch resistance of the coating film is good.

The radical polymer (B) preferably has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of 500 to 100,000, more preferably 1,000 to 95,000. When the Mw of the radical polymer (B) is within the above range, the coatability, appearance, strength, hardness and scratch resistance of the coating film (cured film) are excellent.

The SP value of the radical polymer (B) is, for example, 7.0 to 9.5, preferably 8.0 to 9.0, more preferably 8.2 to 8.9.

When the SP value of the radical polymer (B) is within the above range, the compatibility with the amino resin (A) is improved, and the scratch resistance of the cured film described later can be improved.

The difference between the SP value of the amino resin (A) and the SP value of the radical polymer (B) is, for example, ±3 or less, preferably ±1.3 or less, more preferably ±1.0 or less. , more preferably ±0.5 or less.

Examples of commercially available products of the radical polymer (B) include "NISSO-PB GI-1000", "NISSO-PB GI-2000", "NISSO-PB GI-3000" and "NISSO" manufactured by Nippon Soda Co., Ltd. -PB G-1000", "NISSO-PB G-2000", "NISSO-PB G-3000", "Krasol LBH-P2000" and "Krasol HLBH-P2000" manufactured by CRAY VALLEY.

<Acid catalyst (C)>
Various known acid catalysts (C) can be used without particular limitation. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids. Examples of the organic acids include carboxylic acids such as oxalic acid, acetic acid and formic acid; organic sulfonic acids such as acid, hexadecanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cumenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, nonylnaphthalenesulfonic acid; methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate , isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di- Organic phosphoric acids such as 2-ethylhexyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and bisnonylphenyl acid phosphate; thermal acid generators such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts agents and the like. These can be used singly or in combination of two or more.

The acid catalyst (C) is preferably p-toluenesulfonic acid from the viewpoint of good compatibility with the amino resin (A), the radical polymer (B) and the dilution solvent described below.

The content of the acid catalyst (C) in the composition of the present invention is not particularly limited, but from the viewpoint of achieving both rapid curing and storage stability of the coating material described later, the amino resin (A) and the radical polymer It is preferably about 1 to 10 parts by mass, more preferably about 2 to 8 parts by mass, per 100 parts by mass of (B).

<Fluorine-Containing Surface Conditioner (D)>
The composition of the present invention preferably further contains a fluorine-containing surface conditioner (hereinafter also referred to as "fluorine-containing surface conditioner (D))").

The fluorine-containing surface conditioner (D) is a hydrophilic surfactant, and has, for example, a perfluoroalkyl group and a hydroxyl group.

The carbon number of the perfluoroalkyl group is, for example, 3-20, preferably 4-6. A perfluoroalkyl group is located, for example, at one molecular terminal of the fluorine-containing surface conditioner (D). The hydroxyl group is located, for example, at the other molecular terminal of the fluorine-containing surface conditioner (D).

Specific examples of fluorine-containing surface conditioners (D) include perfluoroalkylethylene oxide adducts.

The fluorine-containing surface conditioner (D) can be used alone or in combination of two or more.

Among fluorine-containing surface conditioners (D), perfluoroalkylethylene oxide adducts are preferred.

Commercially available fluorine-containing surface conditioners (D) include "Surflon IF-HC125" and "Surflon S-242" manufactured by AGC Seimi Chemical.

The content of the fluorine-containing surface conditioner (D) is, for example, 0.05 to 40 parts by mass, preferably 0, per 100 parts by mass of the total of the amino resin (A) and the radical polymer (B). .1 to 30 parts by mass, more preferably 0.1 to 3 parts by mass.

When the content of the fluorine-containing surface conditioner (D) is within the above range, it is possible to reduce the contact angle of water on the cured film, which will be described later. can be granted.

The composition of the present invention may also contain a fluorine-free surface conditioner. Examples of fluorine-free surface conditioners include silicone-based surfactants and sulfonic acid-based surfactants. Fluorine-free surface conditioners can be used alone or in combination of two or more. A fluorine-free surface conditioner may be used in combination with the fluorine-containing surface conditioner (D). The content range of the fluorine-free surface conditioner is the same as the content range of the fluorine-containing surface conditioner (D).

<Additive (E)>
The composition of the present invention may contain an additive (E) as necessary. Such additives are not particularly limited as long as they do not impair the effects of the present invention, and known additives can be used. Specifically, pigments, dyes, leveling agents, adhesion promoters, stability improvers, foaming inhibitors, weather resistance improvers, popping inhibitors, antioxidants, dispersants, wetting agents, thixotropic agents, UV absorbers, etc. is mentioned. Additives (E) may contain Lewis acids and protonic acids that do not fall under the category of acid catalysts (C). Moreover, the additive (E) may be used alone or in combination of two or more.

The content of the additive (E) is usually 0 to 50 parts by mass, preferably 0 to 30 parts by mass, per 100 parts by mass of the composition of the present invention. When the content of the additive (E) is within the above range, a thermosetting resin composition having excellent coatability, coating properties and storage stability can be obtained.

<Solvent>
The composition of the invention may be diluted with a solvent if desired. The solvent (diluting solvent) is not particularly limited as long as it does not impair the effects of the present invention. Acetate ester solvents, ketone solvents such as dioxane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1-methoxy-2-propanol (PGM), etc. and water. The solvents may be used singly or in combination of two or more.

From the viewpoint of the solubility of the amino resin (A), the radical polymer (B), and the acid catalyst (C), it is preferable to use solvents with relatively low polarity, such as methyl ethyl ketone, toluene, xylene, and cyclohexanone. .

When the composition of the present invention is diluted with a solvent, the content of the entire solvent is preferably 10 to 95% by mass, more preferably 20.0 to 90.0% by mass, based on the total amount of the diluent of the composition. %, more preferably 40.0 to 85.0% by mass.

The thermosetting resin composition described above contains an alkyl-etherified amino resin having an SP value of 10.0 or less, a radical polymer having a hydroxyl group, and an acid catalyst. Therefore, it is possible to form a cured film having excellent adhesion to the substrate described below.

The composition of the present invention can be suitably used for paint (coating material) applications. Specific applications of the thermosetting resin composition include coating materials for printing.

The printing coating material contains a thermosetting resin composition. Printing coatings are applied to a substrate as a pre-printing treatment and then cured to improve the printability of the substrate for inks.

[Cured product and laminate]
The cured product of the present invention is characterized by comprising the composition of the present invention, and is usually in the form of a cured film. Further, the laminate of the present invention is characterized by comprising a cured film made of the composition of the present invention. Examples include a laminate comprising a substrate and a cured film formed on the substrate, a substrate, Examples include a laminate in which a cured film and a printed layer are laminated in this order.

The method for producing the cured product (cured film) of the present invention includes a step of heating the composition of the present invention to a temperature of 60 to 160° C., preferably 70 to 140° C. (hereinafter also referred to as “heating step”). ).

The heating time in the heating step depends on the heating temperature, but is in the range of 20 seconds to 60 minutes, preferably 30 seconds to 40 minutes. Temperature and time can be appropriately combined according to nature.

After the step of applying the composition of the present invention to a substrate (object to be coated), the composition is heated (dried) under the same conditions as in the heating step and cured to form a cured film. Inventive laminates can be manufactured.

The heating may be performed in two or more steps, and the laminate cured within the ranges of temperature and time described above may be transferred to another heat-retaining chamber and subjected to a post-curing step such as separate heating. The heating step may be performed under reduced pressure or under an inert gas atmosphere.

From the viewpoint of excellent printability of the printed layer formed on the cured film, the contact angle of water of the cured film (cured product) is, for example, 20 to 90°, preferably 20 to 89°, more preferably 50 to 89°, more preferably 60 to 85°. The contact angle can be measured according to the method described in Examples below.

Examples of the base material (body to be coated) include resin materials, and the resin materials include vinyl chloride, polyethylene terephthalate, olefin polymers (e.g., polyethylene, polypropylene, etc.), polycarbonate, ABS, PMMA, nylon, and polyamide. and those surface-treated to these. Further, substrates made of these materials may be coated with a primer, an intermediate coating, and a top coating as required. Among such substrates, substrates made of olefin polymers are preferred. A cured film made of the composition of the present invention is particularly excellent in adhesion to a substrate made of an olefin polymer, and is also excellent in appearance, scratch resistance and printability.

The method of applying the composition of the present invention to a substrate is not particularly limited, and includes a spray coating method, a dip coating method, a roll coating method, a gravure coating method, a spin coating method, and a method using a bar coater or doctor blade. etc.

The thickness of the cured film is not particularly limited, and may be appropriately selected according to the desired application.

Examples of applications of the above-described laminate include product labels, RFID tags, stickers, and the like, preferably product labels.

As shown in FIG. 1, the product label 1 includes a substrate 2, a coat layer 3, and a print layer 4 in this order. In other words, the product label 1 includes a laminate in which the substrate 2, the coat layer 3 and the print layer 4 are laminated in order.

The base material 2 is, for example, a resin base material made of the resin material described above.

The coat layer 3 is located on one surface of the base material 2 in the thickness direction. The coat layer 3 is the above-described cured film and includes a cured product obtained by curing the above-described thermosetting composition. In order to prepare the coat layer 3, the above-described printing coating material is applied onto the substrate 2 by the above-described coating method, and then the coating film of the printing coating material is heated to the above-described heating temperature to cure.

The print layer 4 is located on the opposite side of the base material 2 with respect to the coat layer 3 . The print layer 4 is located on one surface of the coat layer 3 in the thickness direction. The print layer 4 is printed, for example, using a known ink by a known printing device.

As shown in Figures 2A and 2B, the product label 1 preferably has an adhesive area 2A and a non-adhesive area 2B.

The adhesive region 2A has adhesive strength (pressure-sensitive adhesive strength). The adhesive region 2A is located on the other surface of the base material 2 in the thickness direction. The adhesive region 2A is an adhesive layer (pressure-sensitive adhesive layer) formed from a known adhesive (pressure-sensitive adhesive). The position of the adhesive area 2A is appropriately changed according to the application.

The non-adhesive region 2B does not have adhesive strength (pressure-sensitive adhesive strength). The non-adhesive area 2B is a portion other than the adhesive area 2A on the other surface of the substrate 2 in the thickness direction. The other surface in the thickness direction of the base material 2 is exposed in the non-adhesive area 2B.

Examples of such a product label 1 include a sticking label 11 (see FIG. 2A) that is directly attached to the product, and a wrapping label (wrap round) 12 (see FIG. 2B) that is wrapped around the product.

As shown in FIG. 2A, the adhesive region 2A of the sticky label 11 is positioned, for example, in the center of the other surface of the substrate 2 in the thickness direction. As shown in FIG. 2B, the adhesive region 2A of the torso band label 12 is positioned, for example, at the end of the other surface of the substrate 2 in the thickness direction.

EXAMPLES The present invention will be explained more specifically by showing Examples below, but the present invention is not limited to them. Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical properties, parameters, etc., can be replaced with the upper limit value (values defined as “less than” or “less than”) or lower limit value (values defined as “greater than” or “exceeding”). can. "Parts" and "%" are based on mass unless otherwise specified.

[Physical properties]
Methods for measuring physical properties of materials used in Examples and Comparative Examples are as follows.

<Weight average molecular weight>
The weight average molecular weights (Mw) of amino resin (A) and radical polymer (B) were measured by GPC under the following conditions.
Apparatus: Shodex GPC-101 manufactured by Showa Denko K.K.
Detector: RI-71S
Column: GPC KF804L (Φ8.0 mm × 300 mm) × 3 manufactured by Showa Denko K.K. Measurement temperature: 40°C
Eluent: THF (tetrahydrofuran)
Flow rate: 1.0ml/min
<Hydroxyl value>
The hydroxyl value of the radical polymer (B) having a hydroxyl group was measured according to JIS K 1557-1 (determination of hydroxyl value).

[Synthesis example]
<Synthesis Example 1> Synthesis of radical polymer having hydroxyl group 2.4 kg of styrene/ethylene/1-butene/styrene copolymer was added to 10 L of toluene, heated to 112°C under a nitrogen atmosphere, and 4 L of toluene was distilled. let me out After raising the temperature to 165° C., 266 g of 2-hydroxypropyl acrylate and 67 g of di-tert-butyl peroxide were supplied to the system over 6 hours while stirring, followed by stirring at 165° C. for 1.5 hours. After cooling, toluene was supplied to the system to adjust the solid content to 22% by mass.

The resulting 2-hydroxypropyl acrylate-modified styrene/ethylene/1-butene/styrene copolymer had a hydroxyl value of 40 mgKOH/g and an Mw of 90,000.

<Synthesis Example 2> Synthesis of radical polymer having hydroxyl group 2.3 kg of styrene/ethylene/propylene/styrene copolymer was added to 10 L of toluene, heated to 112°C under a nitrogen atmosphere, and 4 L of toluene was distilled off. rice field. After raising the temperature to 165° C., 265 g of 2-hydroxypropyl acrylate and 74 g of di-tert-butyl peroxide were supplied to the system over 5 hours while stirring, followed by stirring at 165° C. for 2 hours. After cooling, toluene was supplied to the system to adjust the solid content to 18% by mass.

The resulting 2-hydroxypropyl acrylate-modified styrene/ethylene/propylene/styrene copolymer had a hydroxyl value of 50 mgKOH/g and an Mw of 80,000.

<Synthesis Example 3> Synthesis of radical polymer containing no hydroxyl group 3 kg of a propylene/1-butene copolymer was added to 10 L of toluene and heated to 145°C under a nitrogen atmosphere to dissolve the copolymer in toluene. rice field. Further, while stirring, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours, followed by stirring at 145° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer, filtered, washed with acetone, and dried in vacuum. A mixed solution of toluene and MEK was supplied to the system so that the resulting polymer had a solid content of 10% by mass.

Mw of the resulting maleic anhydride-modified propylene/1-butene copolymer was 110,000.

[material]
In Examples and Comparative Examples, raw materials used in preparing the compositions (coating materials) and substrates used in applying the compositions are as follows.

<Alkyl etherified amino resin (A)>
(A-1) Butyl etherified melamine resin: "Uban 520" (manufactured by Mitsui Chemicals, Inc.)
・ Solid content: 85% by mass
・Weight average molecular weight: 1,800
・ SP value: 9.2
(A-2) Butyl etherified melamine resin: "Uban 20SB" (manufactured by Mitsui Chemicals, Inc.)
・ Solid content: 50% by mass
・Weight average molecular weight: 5,500
・ SP value: 9.3
<Alkyl etherified amino resin (A') other than amino resin (A)>
(A'-1) Butyl etherified melamine resin: "Uban 225" (manufactured by Mitsui Chemicals, Inc.)
・ Solid content: 60% by mass
・Weight average molecular weight: 2,200
・ SP value: 10.2
(A'-2) Methyl etherified melamine resin: "Cymel 303LF" (manufactured by Daicel Allnex)
・ Solid content: 98% by mass
・Weight average molecular weight: 900
・ SP value: 13.8
<Radical polymer having hydroxyl group (B)>
(B-1) Radical polymer obtained in Synthesis Example 1 Solid content: 22% by mass
・Weight average molecular weight: 90,000
・Hydroxyl value: 50mgKOH/g
・ SP value: 8.8
<Radical polymer having hydroxyl group (B)>
(B-2) Radical polymer obtained in Synthesis Example 2 Solid content: 16% by mass
・Weight average molecular weight: 80,000
・Hydroxyl value: 40mgKOH/g
・ SP value: 8.9
(B-3) Hydrogenated hydroxyl-containing butadiene polymer “NISSO-PB GI-1000” (manufactured by Nippon Soda Co., Ltd.)
・ Solid content: 100% by mass
・Weight average molecular weight: 4,400
・Hydroxyl value: 73mgKOH/g
・ SP value: 8.6
<Radical polymer (B′) other than radical polymer (B)>
(B'-1) Radical polymer obtained in Synthesis Example 3 Solid content: 10% by mass
・Weight average molecular weight: 110,000
・ SP value: 8.8
(B'-2) Butadiene polymer containing no hydroxyl group "NISSO-PB BI-2000" (manufactured by Nippon Soda Co., Ltd.)
・ Solid content: 100% by mass
・Weight average molecular weight: 4,500
・ SP value: 9.0
<Acid catalyst (C)>
(C-1) "Para-toluenesulfonic acid monohydrate" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
<Surface conditioner (D)>
(D-1) Fluorine-containing surface conditioner "Surflon IF-HC125" (manufactured by AGC Seichemical Co., Ltd.)
(D-2) Fluorine-containing surface conditioner "Surflon S-242" (manufactured by AGC Seichemical Co., Ltd.)
(D-3) Silicone-based surface conditioner “BYK-3560” (manufactured by BYK Co., Ltd.)
(D-4) Sulfonic acid-based surface conditioner "Pelex TR" (manufactured by Kao Corporation)
<Base material>
・ Biaxially stretched polypropylene film (210 mm x 297 mm x thickness 50 μm)
[Evaluation items and evaluation methods]
Coating films (cured films) prepared in Examples and Comparative Examples were evaluated as follows.

<Appearance of coating film>
The haze of the cured film immediately after curing was measured with a haze meter (NDH-4000 type, manufactured by Nippon Denshoku Industries Co., Ltd.). Also, the test piece obtained by curing the resin composition was visually evaluated according to the following criteria.
A: No foreign matter or whitening was observed, and no abnormalities were observed (◯).
B: Foreign matter and whitening are observed, and there is an abnormality (x).

<Adhesion>
According to JIS K5400 8.5.2: 1990, use a knife on the coating film (cured film) to make vertical and horizontal cuts with a width of 1 mm to reach the substrate, and then cellophane on the surface A pressure-sensitive adhesive tape was adhered to the adhesive tape, and the state of the coating film after instantaneous peeling was evaluated according to the following criteria.
A: No peeling or chipping of the coating film (◯).
B: Partial peeling and chipping of the coating film (Δ).
C: Peeling and chipping of the coating film are present on the entire surface (×).

<Scratch resistance>
The cured film immediately after curing was rubbed once with steel wool (Bonstar No. 0000, manufactured by Nippon Steel Wool Industry Co., Ltd.), and then the state of the coating film (cured film) was evaluated according to the following criteria.
A: The number of scratches is 0 to 5 (◯).
B: The number of scratches is 6 to 10 (Δ).
C: The number of scratches is 11 or more (x).

<Printability>
The adhesion of the ink (copolymer of vinyl acetate and vinyl chloride) printed on the cured film and the contact angle of water to the cured film were measured. Ink adhesion was evaluated according to JIS K5400 8.5.2:1990. The contact angle of water was measured in accordance with JIS R3257:1999 "Method for testing wettability of substrate glass surface". Then, printability was evaluated according to the following criteria.
A: The contact angle of water is 89° or less, and there is no peeling or chipping of the ink (⊚).
B: The contact angle of water is 90° or more, and there is no peeling or chipping of the ink (◯).
C: The contact angle of water is 89° or less, and there is some peeling and chipping of the ink (Δ).
D: The contact angle of water is 90° or more, and the ink is partially peeled off or chipped (Δ).
E: The contact angle of water is 89° or less, and the ink is peeled off and chipped over the entire surface (x).
F: The contact angle of water is 90° or more, and the ink is peeled off and chipped over the entire surface (x).

[Example 1]
20.2 g of the amino resin solution (A-1) and 52.0 g of the radical polymer solution (B-1) were blended, and 22.2 g of a toluene/MEK = 50/50 mixed solvent was added to dissolve and mix thoroughly. bottom. Next, 5.7 g of a solution of the acid catalyst (C-1) with PGM having a solid content of 25% (5 mass parts per 100 mass parts of the total of the amino resin (A-1) and the radical polymer (B-1) Part) was added to prepare a thermosetting resin composition having a non-volatile content of 30% by mass. The resulting composition was applied to an OPP film having a thickness of 50 μm with a bar coater #14, and heated in a hot air dryer for 120 seconds and 1 minute to form a cured film having a thickness of about 3 μm. Various tests were conducted. Table 1 shows the results.

[Examples 2 to 6, 11 to 13, Comparative Examples 1 to 6]
A thermosetting resin composition was prepared in the same manner as in Example 1, except that the compositions shown in Tables 1 to 3 were used. Tables 1 to 3 show the results of various tests.

[Example 7]
A thermosetting resin composition was prepared in the same manner as in Example 3, except that 0.5 parts by mass of the surface conditioner (D-1) was added to the thermosetting resin composition. Table 2 shows the results of various tests.

[Example 8]
The radical polymer solution (B-1) was changed to the radical polymer solution (B-2), and 0.5 parts by mass of the surface conditioner (D-2) was added to the thermosetting resin composition. A thermosetting resin composition was prepared in the same manner as in Example 3, except for the above. Table 2 shows the results of various tests.

[Example 9]
The radical polymer solution (B-1) was changed to the radical polymer solution (B-3), and 0.5 parts by mass of the surface conditioner (D-3) was added to the thermosetting resin composition. A thermosetting resin composition was prepared in the same manner as in Example 3, except for the above. Table 2 shows the results of various tests.

[Example 10]
A thermosetting resin composition was prepared in the same manner as in Example 9, except that the surface modifier (D-3) was changed to the surface modifier (D-4). Table 2 shows the results of various tests.

[Example 14]
A thermosetting resin composition was prepared in the same manner as in Example 12, except that 0.5 parts by mass of the surface conditioner (D-1) was added to the thermosetting resin composition. Table 2 shows the results of various tests.

[Example 15]
A thermosetting resin composition was prepared in the same manner as in Example 13, except that 0.5 parts by mass of the surface conditioner (D-2) was added to the thermosetting resin composition. Table 2 shows the results of various tests. The compositions in Tables 1 to 3 are all converted to solid content.

なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれる。

It should be noted that although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an illustration and should not be construed as a limitation. Variations of the invention that are obvious to those skilled in the art are included in the following claims.

INDUSTRIAL APPLICABILITY The thermosetting resin composition of the present invention can be used for various industrial products, and can be suitably used for paint (coating material) applications, for example. The cured product and laminate of the present invention can be used for various industrial products, and can be suitably used for product labels, for example.

REFERENCE SIGNS LIST 1 product label 2 base material 2A adhesive area 2B non-adhesive area 3 coating layer 4 printing layer

Claims (15)

(A) an alkyl etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less;
(B) a radical polymer having a hydroxyl group;
(C) an acid catalyst ,
The thermosetting resin composition, wherein the mass ratio of the alkyl etherified amino resin to the radical polymer is in the range of 1/99 to 49/51. (A) an alkyl etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less;
(B) a radical polymer having a hydroxyl group;
(C) an acid catalyst,
A thermosetting resin composition, wherein the radical polymer has a solubility parameter δ (SP value) of 8.0 to 9.0. (A) an alkyl etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less;
(B) a radical polymer having a hydroxyl group;
(C) an acid catalyst,
The radical polymer is a reaction product of a radical polymer having no hydroxyl group and a monomer having a hydroxyl group,
The radical polymer having no hydroxyl group is a group consisting of olefin polymers having 2 to 20 carbon atoms, olefin polymers having a plurality of double bonds, and copolymers of olefins and other radically polymerizable monomers. A thermosetting resin composition, which is at least one polymer selected from (A) an alkyl etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less;
(B) a radical polymer having a hydroxyl group;
(C) an acid catalyst,
A thermosetting resin composition further comprising (D) a fluorine-containing surface conditioner in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the total of the alkyl etherified amino resin and the radical polymer. 5. The thermosetting resin composition according to any one of claims 2 to 4 , wherein the mass ratio of said alkyl etherified amino resin to said radical polymer is in the range of 50/50 to 99/1. The thermosetting resin composition according to any one of claims 1 to 5 , wherein the alkyl-etherified amino resin is a butyl-etherified melamine resin. The thermosetting resin composition according to any one of claims 1 to 6 , wherein the radical polymer has a hydroxyl value of 20 to 200 mgKOH/g. The thermosetting resin composition according to any one of claims 1 to 7, wherein the acid catalyst is p-toluenesulfonic acid. including a thermosetting resin composition ,
The thermosetting resin composition comprises (A) an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less, (B) a radical polymer having a hydroxyl group, and (C) an acid catalyst. A coating material for printing , comprising : A cured product comprising the thermosetting resin composition according to any one of claims 1 to 8 . Consisting of a thermosetting resin composition ,
The thermosetting resin composition comprises (A) an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less, (B) a radical polymer having a hydroxyl group, and (C) an acid catalyst. , contains
A cured product having a water contact angle of 20 to 89°. A laminate in which a base material, a cured film and a printed layer are laminated in this order,
The cured film includes a cured product of a thermosetting resin composition,
The thermosetting resin composition comprises (A) an alkyl-etherified amino resin having a solubility parameter δ (SP value) of 10.0 or less, (B) a radical polymer having a hydroxyl group, and (C) an acid catalyst. A laminate containing 13. The laminate according to claim 12 , wherein said substrate comprises an olefin polymer. comprising a laminate according to claim 12 or 13 ,
A label, wherein the substrate includes a sticky region and a non-sticky region. After the step of applying the thermosetting resin composition according to any one of claims 1 to 8 to the substrate,
A method for producing a laminate, comprising a step of heating the thermosetting resin composition to 60 to 160° C. to cure it to form a cured film.

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