TW202130743A - Thermosetting resin composition, coating material for printing, cured product, laminate, and method for producing laminate - Google Patents

Abstract

This thermosetting resin composition contains (A) an alkyl etherified amino resin having a solubility parameter [delta](SP value) of at most 10.0, (B) a radical polymer having a hydroxyl group, and (C) an acid catalyst.

Description

Thermosetting resin composition, printing coating material, cured product, laminate, and method of manufacturing laminate

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

OPP (biaxially stretched polypropylene film) used as the base material for sealing or labeling has low surface free energy, for example, the contact angle of water is more than 100∘, so the ink is not suitable for printing. Therefore, the printing suitability of the ink is usually improved by forming the easy-printable layer on the OPP. However, due to the insufficient scratch resistance of the easy-printable layer, it is easy to damage the easy-to-print layer during handling and destroy the design. The problem.

In addition, in Patent Document 1, as a thermosetting release coating agent that has excellent appearance of the coating film, and can form a cured film with excellent peeling performance and solvent resistance, it discloses a melamine resin (A) with a carbon number of 12 to 24. A self-condensate of aliphatic hydroxycarboxylic acid (B) and a thermosetting release coating agent for acid catalyst (C), and it is revealed that the coating agent may further contain polyol (D) such as polyolefin polyol .

In addition, Patent Document 2 discloses a coating solution containing an initial polymer of hexamethylolmelamine as a coating solution for forming an easy-to-print layer (refer to the examples of Patent Document 2). Furthermore, the cited document 2 is to apply a coating liquid on the surface of a resin substrate, heat the coating liquid to form a cyanuric acid resin layer, and then use an aqueous ink to perform image printing on the melamine resin layer. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2019-94483 Patent Document 2: Japanese Patent Laid-Open No. 2019-64238

(The problem to be solved by the invention)

However, Patent Document 1 does not include an example in which a melamine resin and a polyolefin polyol are combined, nor does it describe the special effects caused by the combination of a melamine resin and a polyolefin polyol. In addition, the inventors of the present invention used the methylated melamine resin used in the examples of Patent Document 1 to test with an olefin polymer. As a result, it was found that the obtained cured film had low transparency and was not practical.

In addition, Patent Document 2 forms a melamine resin layer on the surface of the resin substrate as an easy-to-print layer, but there are cases where the adhesion of the melamine resin layer to the resin substrate is insufficient.

The subject 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 with excellent adhesion. (Technical means to solve the problem)

After intensive research, the inventors found that by using alkyl etherified amino resin with solubility parameter δ (SP value) of 10.0 or less, radical polymer with hydroxyl group, and thermosetting resin with acid catalyst The composition can solve the above-mentioned problems.

That is, the present invention includes the following aspects.

The present invention [1] includes a thermosetting resin composition containing (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, With (C) acid catalyst.

The present invention [2] is the thermosetting resin composition including the above [1], 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] is the thermosetting resin composition including the above [1], wherein the mass ratio of the alkyl etherified amino resin to the radical polymer is 1/99 to 49/51.

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

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

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

The present invention [7] is a thermosetting resin composition comprising any one of the above [1] to [6], wherein the radical polymerization system does not have a hydroxyl radical polymer and a monomer having a hydroxyl radical is produced by the reaction The above-mentioned radical polymer without a hydroxyl group is selected from the group consisting of a polymer of olefins with 2 to 20 carbon atoms, a polymer of olefins with multiple double bonds, and copolymers of olefins and other radical polymerizable monomers. At least one aggregate of the group.

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

The present invention [9] is a thermosetting resin composition comprising any one of the above [1] to [8], which is further based on 100 masses of the total of the alkyl etherified amino resin and the radical polymer Parts, containing 0.1-30 parts by mass of (D) fluorine-containing surface regulator.

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

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

The present invention [12] includes the cured product of [11] above, wherein the contact angle of water is 20~89∘.

The present invention [13] includes a laminate in which a substrate, a cured film, and a printing layer are laminated in this order, and the cured film contains the cured product of [11].

The present invention [14] is the laminate including the above-mentioned [13], wherein the base material is composed of an olefin polymer.

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

The present invention [16] includes a method for manufacturing a laminate, which includes the step of applying the thermosetting resin composition of any one of [1] to [9] to a substrate, and then curing the thermosetting resin The step of heating the resin composition to 60 to 160°C to harden it to form a cured film. (Compared to the effect of the previous technology)

Since the thermosetting resin composition of the present invention contains an alkyl etherified amino resin with an SP value of 10.0 or less, a radical polymer having a hydroxyl group, and an acid catalyst, it can form a cured film with excellent adhesion.

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

Since the cured product of the present invention is composed of the above-mentioned thermosetting resin composition, it has superior adhesion.

Since the laminate of the present invention includes a cured film containing the above-mentioned cured product, the adhesiveness of the cured film to the base material can be improved.

Since the label of the present invention contains the above-mentioned laminate and the substrate includes an adhesive area and a non-adhesive area, the adhesiveness of the cured film to the substrate can be improved, and the label can be attached to an object.

The manufacturing method of the laminated body of this invention can manufacture the said laminated body smoothly.

The thermosetting resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains (A) an alkyl etherified amino resin with a solubility parameter δ (SP value) of 10.0 or less, and (B) has Hydroxyl radical polymer, and (C) acid catalyst. The details of each component are shown below.

＜Alkyl etherified amino resin (A)＞ The alkyl etherified amino resin (A) (hereinafter also referred to as "amino resin (A)") used in the present invention is an alkyl etherified amino resin with a solubility parameter δ (SP value) of 10.0 or less. Alkyl etherified amino resin refers to 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 (for example, methyl etherified , Ethyl etherification, propyl etherification, n-butyl etherification, isobutyl etherification, etc.) of the amino resin.

The above-mentioned SP value is generally referred to as the solubility parameter among those with ordinary knowledge in the technical field of the present invention. It is a measure of the degree of hydrophilicity or hydrophobicity of the resin, and is used to judge the compatibility between resins. It is also an important measure. The solubility parameter can be numerically quantified based on, for example, a turbidimetry method (reference: K. W. Suh, D. H. Clarke J. Polymer. Sci., A-1, 5, 1671 (1967).). The solubility parameter in this manual is the parameter obtained by the turbidimetric method. The solubility parameter obtained by the turbidity measurement method, for example, after the solid content (predetermined mass) of the resin to be measured is dissolved in a certain amount of good solvent (acetone, etc.), the resin is insolubilized by dropping water or a poor solvent such as hexane , The respective titration amount until turbidity occurs in the solution can be obtained by the well-known calculation method described in the above-mentioned references.

The SP value of the aforementioned amino resin (A) is 10.0 or less, preferably in the range of 9.0 to 9.8, more preferably in the range of 9.1 to 9.5. When the SP value of the above-mentioned amino resin (A) is within the above-mentioned range, the compatibility with the radical polymer (B) described later becomes good, and the appearance, adhesion to the polyolefin substrate, and resistance to Coating film (cured film) with excellent scratch resistance and printability.

As a preferable example of the above-mentioned amino resin (A), from the viewpoint of excellent compatibility with the radical polymer (B) having a hydroxyl group, for example, a butyl etherified melamine resin may be mentioned. Base type butyl etherified melamine resin.

The said amino resin (A) can be used individually or in combination of 2 or more types.

As a commercially available product of the aforementioned amino resin (A), butyl etherified melamine resins such as "U-VAN 20SB" and "U-VAN520" manufactured by Mitsui Chemicals Co., Ltd. can be used.

The weight average molecular weight of the amino resin (A) measured by GPC (gel permeation chromatography) in terms of polystyrene is preferably 1,000 to 8,000, more preferably 1200 to 7000, more preferably 1,500 ~6,000. In addition, the weight average molecular weight can be measured according to the method described in the below-mentioned Examples (the same applies hereinafter). When the weight average molecular weight of the amino resin (A) is in the above range, a resin composition with moderate viscosity can be obtained, and a cured product with excellent compatibility, mechanical properties, smoothness, and appearance can be obtained.

The above-mentioned amino resin (A) is preferably obtained by condensing melamine, formaldehyde, and an alcohol having an alkyl chain with a carbon number of 1 to 6 in the presence of an acid catalyst. As the above-mentioned alcohol, for example, methanol, ethanol, propanol, n-butanol, isobutanol, etc. can be used. As the alcohol, a water-containing alcohol can also be used, or a so-called mixed alcohol containing a small amount of other alcohols different from the main alcohol can be used.

The above-mentioned melamine is not particularly limited, and it can be synthesized according to a conventionally known method, or it may be a commercially available product. The above-mentioned formaldehyde may be an aqueous solution or solid trioxane. From the viewpoint of economic efficiency, para-formaldehyde having a formaldehyde concentration of 80% by mass or more is preferable.

The mass ratio of the solid content 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 10/90~95/5. When the content of the amino resin (A) is within the above range, the adhesion to the base material of the cured film can be reliably improved.

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

In addition, from the viewpoint of printing suitability, the solid content of the amino resin (A) relative to the radical polymer (B) is preferably 1/99~49/51, and more preferably 10/90~40/ 60. If the mass ratio of the solid content of the amino resin (A) to the radical polymer (B) is in the above range, the cured film can be reliably imparted with superior printing suitability for ink.

In addition, from the viewpoint of the balance between scratch resistance and printing suitability, the solid content of the amino resin (A) relative to the radical polymer (B) is preferably 20/80 to 70/30, more preferably 20/80~60/40.

＜Free radical polymer with hydroxyl group＞ The radical polymer (B) with hydroxyl group used in the present invention (hereinafter also referred to as "radical polymer (B)") is modified by changing the radical polymer without hydroxyl group with monomer having hydroxyl group. Quality. In other words, the radical polymer having a hydroxyl group (B) is a reaction product of a radical polymer having no hydroxyl group and a monomer having a hydroxyl group. In addition, the radical polymer which does not have a hydroxyl group is referred to as the radical polymer before modification, and it is distinguished from the radical polymer (B) which has a hydroxyl group in the following.

The polymer of the radical polymerizable monomer of the radical polymerization system before modification is preferably a polymer of a radical polymerizable monomer containing at least an olefin (olefin-based polymer). Olefin is an example of a radically polymerizable monomer.

As the radical polymer (olefin polymer) before modification, for example, a polymer of an olefin having 2 to 20 carbon atoms, a polymer of an olefin having a plurality of double bonds, an olefin and other radical polymerizable monomers Copolymer. In other words, the radical polymer that does not have a hydroxyl group is selected from, for example, a polymer of an olefin having 2 to 20 carbon atoms, a polymer of an olefin having a plurality of double bonds, and a copolymer of an olefin and other radical polymerizable monomers. At least one kind of olefin-based polymer of the constituent group.

The polymer of an olefin having 2 to 20 carbon atoms specifically contains a structural unit derived from an α-olefin having 4 to 20 carbon atoms. That is, the polymerization system of olefins with 2 to 20 carbons is a homopolymer composed of α-olefins with 4 to 20 carbons, or the copolymerization of α-olefins with 4 to 20 carbons and olefins with 2 to 3 carbons. Fit.

Examples of α-olefins with 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1 -Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other linear or branched α-olefins.

As the α-olefin having 4 to 20 carbon atoms, preferably, for example, linear olefin having 4 to 10 carbon atoms, more preferably linear olefin having 4 to 6 carbon atoms, and more preferably 1-butene. If 1-butene is used as an α-olefin with 4 to 20 carbon atoms, good solvent solubility and superior resin strength can be achieved. These can be used alone or in combination of two or more kinds.

Examples of the olefin having 2 to 3 carbon atoms include ethylene and propylene, and propylene is preferred.

Examples of olefins having 2 to 20 carbon atoms include the aforementioned olefins having 2 to 3 carbon atoms, and the aforementioned α-olefins having 4 to 20 carbon atoms. These can be used alone or in combination of two or more kinds. As the olefin having 2 to 20 carbon atoms, preferably, for example, ethylene, propylene, and 1-butene are used, and more preferably, for example, a combination of propylene and 1-butene is used.

Specifically, the polymer of an olefin having a plurality of double bonds contains a structural unit derived from an olefin having a plurality of double bonds.

Examples of olefins having a plurality of double bonds include diolefins, triolefins, and tetraolefins. Specific examples of olefins having a plurality of double bonds include 1,2-butadiene, 1,3-butadiene, 3-methyl-1,2-butadiene, 2-methyl-1,3 -Butadiene, 1,5-hexadiene, etc. From the viewpoint of superior compatibility with the amino resin (A) or the diluent solvent described later, 1,3-butadiene is preferably used.

Specifically, the copolymer of an olefin and another radical polymerizable monomer contains a constituent unit derived from the above-mentioned olefin and a constituent unit derived from a radical polymerizable monomer other than the olefin.

Examples of radical 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 radical polymers before modification, the copolymers of olefins and other radical polymerizable monomers are preferred, and the copolymers of olefins with 2 to 20 carbon atoms and styrene are more preferred. For example, a copolymer of an olefin with a carbon number of 2 to 6 and styrene can be mentioned.

As a copolymer of olefin with carbon number 2 to 6 and styrene, particularly preferred are styrene/ethylene/1-butene/styrene copolymer and styrene/ethylene/propylene/styrene copolymer.

The single system with hydroxyl group undergoes an addition reaction to the main chain of the free radical polymer before modification. Thereby, the hydroxyl group is introduced into the radical polymer before modification, and the radical polymer (B) which has a hydroxyl group is prepared.

A single system with a hydroxyl group has ethylenically unsaturated double bonds in addition to the hydroxyl group. Examples of the monomer having a hydroxyl group include hydroxyalkyl (meth)acrylate and the like. In addition, examples of (meth)acrylates include methacrylates and acrylates.

Examples of hydroxyalkyl (meth)acrylates include hydroxyalkyl (meth)acrylates having a hydroxyalkyl group with 2 to 4 carbon atoms; specific examples include 2-hydroxyethyl (meth)acrylate , 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, preferably, for example, hydroxypropyl (meth)acrylate.

Hydroxyalkyl (meth)acrylate can be used individually or in combination of 2 or more types.

As the radical polymer (B) with hydroxyl group, particularly preferred are 2-hydroxypropyl acrylate modified styrene/ethylene/1-butene/styrene copolymer, and 2-hydroxypropyl acrylate modified benzene Ethylene/ethylene/propylene/styrene copolymer.

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, and even more preferably 30 to 150 mgKOH/g. In addition, the hydroxyl value can be measured according to the method described in the below-mentioned Examples. If the hydroxyl value is in the above range, the compatibility with the above-mentioned amino resin (A) is good, a clear coating film (cured film) can be obtained, and the scratch resistance of the coating film is good.

The weight average molecular weight (Mw) of the radical polymer (B) measured by GPC in terms of polystyrene is preferably 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 paintability, 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, and more preferably 8.2 to 8.9.

If the SP value of the radical polymer (B) is within the above-mentioned range, the compatibility with the above-mentioned amino resin (A) is good, 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, and still more preferably Less than ±0.5.

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

＜Acid catalyst (C)＞ As the acid catalyst (C), various known substances can be used without particular limitation. Specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, or organic acids. Examples of the organic acids include carboxylic acids such as oxalic acid, acetic acid, and formic acid; methanesulfonic acid, trifluoromethanesulfonic acid, isoprenesulfonic acid, camphorsulfonic acid, hexanesulfonic acid, octanesulfonic acid, nonane Alkane sulfonic acid, decane sulfonic acid, hexadecane sulfonic acid, benzene sulfonic acid, p-toluene sulfonic acid, cumene sulfonic acid, dodecyl benzene sulfonic acid, naphthalene sulfonic acid, nonyl naphthalene sulfonic acid and other organic sulfonic acids ; Methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxy ethyl acid phosphate, octyl acid phosphate, acid phosphoric acid 2-Ethylhexyl ester, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl acid phosphate Base phenyl ester, acid cyclohexyl phosphate, acid phenoxy ethyl phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, acid phosphoric acid Diethyl, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di(2-ethylhexyl) acid phosphate, diisopropyl acid phosphate Organic phosphoric acid such as lauryl ester, distearyl acid phosphate, diphenyl acid phosphate, dinonylphenyl acid phosphate, etc.; thermal oxygen generation of onium salt, benzothiazolium salt, ammonium salt, phosphonium salt, etc.剂 etc. These can be used individually by 1 type or in combination of 2 or more types.

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 diluent solvent described later.

The content of the acid catalyst (C) in the composition of the present invention is not particularly limited. From the viewpoint of achieving both quick-curing properties and storage stability of the coating material described later, it is compared with the above-mentioned amino resin (A) and the above-mentioned The total amount of the radical polymer (B) is 100 parts by mass, preferably about 1-10 parts by mass, more preferably about 2-8 parts by mass.

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

The fluorine-containing surface regulator (D) is a hydrophilic surfactant, such as a perfluoroalkyl group and a hydroxyl group.

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

Specific examples of the fluorine-containing surface regulator (D) include perfluoroalkyl ethylene oxide adducts and the like.

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

Among the fluorine-containing surface regulators (D), preferred examples include perfluoroalkyl ethylene oxide adducts and the like.

As commercially available products of the fluorine-containing surface conditioner (D), "SURFLON IF-HC125", "SURFLON S-242" manufactured by AGC SEIMI CHEMICAL, etc. can be used.

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

If the content of the fluorine-containing surface modifier (D) is within the above range, the water contact angle of the cured film described later can be reduced, and the cured film can be more reliably imparted with superior printing suitability for ink.

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

＜Additive (E)＞ The composition of the present invention may contain an additive (E) if necessary. As such an additive, it is not particularly limited unless the effect of the present invention is impaired, and a known additive can be used. Specific examples include pigments, dyes, leveling agents, dense adhesion imparting agents, stability enhancers, foam inhibitors, weather resistance enhancers, foam inhibitors, antioxidants, dispersants, wetting agents, thixotropic agents, and ultraviolet rays Absorbents, etc. Additive (E) may also contain Lewis acid and protic acid that are not in the category of acid catalyst (C). In addition, the additives (E) may be used singly or in two or more types.

The content of the above-mentioned additive (E) is usually 0-50 parts by mass, preferably 0-30 parts by mass relative to 100 parts by mass of the total amount 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 paintability, coating film physical properties, and storage stability can be obtained.

＜Solvent＞ If necessary, the composition of the present invention can also be diluted with a solvent. The solvent (diluent solvent) is not particularly limited without impairing the effect of the present invention. Examples include alkylbenzene solvents such as benzene, toluene, and xylene; ethyl acetate, propyl acetate, butyl acetate, and pentyl acetate. Acetate-based solvents such as esters and methyl acetylacetate; ketone-based solvents such as diethane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; methanol, ethanol, isopropanol, Alcohol solvents such as 1-butanol, 2-butanol, isobutanol, 1-methoxy-2-propanol (PGM), and water. The above-mentioned solvents may be used singly or in two or more types.

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 a solvent with a lower polarity, such as methyl ethyl ketone, Toluene, xylene, cyclohexanone, etc.

When the composition of the present invention is diluted with a solvent, the content of the above-mentioned solvent as a whole is preferably 10-95% by mass, more preferably 20.0-90.0% by mass, and still more preferably 40.0~ 85.0% by mass.

The above-mentioned thermosetting resin composition 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 superior adhesion to the substrate described later.

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

The coating material for printing contains a thermosetting resin composition. The coating material for printing is applied to the substrate as a pre-printing treatment and then cured to improve the printing suitability of the substrate to the ink.

[Hardened product and laminated body] The cured product of the present invention is characterized by being composed of the composition of the present invention, and is usually in the form of a cured film. In addition, the laminate of the present invention is characterized by containing a cured film composed of the composition of the present invention. For example, a laminate containing a substrate and a cured film formed on the substrate, or a substrate that has been sequentially laminated and cured Laminated body of film and printing layer, etc.

The method for producing a cured product (cured film) of the present invention is characterized by including a step of heating the composition of the present invention to a temperature of 60 to 160°C, preferably 70 to 140°C, and curing it (hereinafter also referred to as "heating step").

The heating time of the above heating step depends on the heating temperature. It is in the range of 20 seconds to 60 minutes, preferably 30 seconds to 40 minutes. It can be matched with the heat resistance of the substrate (coated body) or coating The productivity of the line is the appropriate combination of temperature and time.

After the step of applying the composition of the present invention to the substrate (coated body), the composition is heated (dried) under the same conditions as the above heating step to be cured to form a cured film, thereby making it possible to manufacture The laminated body of the present invention.

Furthermore, heating can be carried out in two or more stages, and the laminated body hardened in the range of temperature and time in the above-mentioned range can be moved to another heat-preserving room, and additional post-curing steps such as heating can be added. The above heating step can be carried out under reduced pressure, or under an inert gas environment.

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 material) is, for example, 20~90∘, preferably 20~89∘, more preferably 50~89 ∘, and more preferably 60~85∘. In addition, the contact angle can be measured according to the method described in the below-mentioned Examples.

Examples of the substrate (coated body) include resin materials, and examples of the resin materials include vinyl chloride, polyethylene terephthalate, and olefin polymers (e.g., polyethylene, polypropylene, etc.), Polycarbonate, ABS, PMMA, nylon, polyamide and those with surface treatment. In addition, among the substrates composed of such materials, those coated with primer, intermediate coating, and top coating can also be used as necessary. Among such substrates, for example, a substrate composed of an olefin polymer is preferable. The cured film composed of the composition of the present invention has excellent adhesion to a substrate composed of an olefin polymer, and also has excellent appearance, scratch resistance, and printability.

The method for applying the composition of the present invention to a substrate is not particularly limited, and examples include spray coating, dip coating, roll coating, gravure coating, spin coating, and the use of bar coaters or doctor blades. The method of the knife and so on.

The thickness of the above-mentioned cured film is not particularly limited, and can be appropriately selected depending on the required application, and is preferably 0.05 to 40 μm, more preferably 0.1 to 30 μm.

Examples of the use of the above-mentioned laminate include labels for products, RFID tags, stickers, etc., and preferably labels for products, for example.

As shown in FIG. 1, the label 1 for a commodity includes a substrate 2, a coating layer 3, and a printing layer 4 in this order. In other words, the label 1 for a product includes a laminate in which the base material 2, the coating layer 3, and the printing layer 4 are laminated in this order.

The substrate 2 is, for example, a resin substrate composed of the above-mentioned resin material.

The coating layer 3 is located on one side of the substrate 2 in the thickness direction. The coating layer 3 is the above-mentioned cured film, and contains a cured product of the above-mentioned thermosetting composition. When preparing the coating layer 3, after coating the coating material for printing on the substrate 2 by the coating method described above, the coating film of the coating material for printing is heated to the heating temperature to be cured.

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

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

The adhesive area 2A has adhesive force (pressure-sensitive adhesive force). The adhesion area 2A is located on the other side of the substrate 2 in the thickness direction. The adhesive region 2A is an adhesive layer (pressure-sensitive adhesive layer) formed of a known adhesive (pressure-sensitive adhesive). The position of the adhesive area 2A is appropriately changed according to the application.

The non-adhesive area 2B has no adhesive force (pressure-sensitive adhesive force). 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. In the non-adhesive area 2B, the other side of the substrate 2 in the thickness direction is exposed.

As such a label 1 for a product, for example, an adhesive label 11 directly attached to a product (see FIG. 2A), a roll label (wrap around) 12 (see FIG. 2B) attached to the product, and the like are mentioned.

As shown in FIG. 2A, the adhesive area 2A in the adhesive label 11 is located at the center of the other surface of the substrate 2 in the thickness direction, for example. As shown in FIG. 2B, the adhesive area 2A in the roll label 12 is located, for example, at the end of the other surface of the substrate 2 in the thickness direction. [Example]

Examples are shown below to explain the present invention more specifically, but the present invention is not limited to these. The specific values of the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the blending ratio (content ratio), physical property values, The upper limit (defined as the value of "below" or "less than full") or the lower limit (defined as the value of "above" or "exceeding") for this record of parameters, etc. In addition, "parts" and "%" are not specifically mentioned before, and both are quality standards.

[Properties] The measurement methods of the physical properties of the materials used in the examples and comparative examples are as follows.

＜Weight average molecular weight＞ The weight average molecular weight (Mw) of the amino resin (A) and the radical polymer (B) is measured by GPC under the following conditions. Installation: Shodex GPC-101 manufactured by Showa Denko Corporation Detector: RI-71S Pillar: GPC KF804L (ϕ8.0mm×300mm) ×3 manufactured by Showa Denko Corporation Measuring temperature: 40℃ Eluent: THF (tetrahydrofuran) Flow rate: 1.0ml/min ＜Hydroxy Value＞ The hydroxyl value of the radical polymer (B) having a hydroxyl group is measured in accordance with JIS K 1557-1 (Method for obtaining the hydroxyl value).

[Synthesis example] <Synthesis example 1> Synthesis of radical polymer with hydroxyl 2.4 kg of styrene/ethylene/1-butene/styrene copolymer was added to 10L of toluene, the temperature was raised to 112°C in a nitrogen environment, and 4L of toluene was distilled out. After the temperature was raised to 165°C, 266 g of 2-hydroxypropyl acrylate and 67 g of di-tert-butyl peroxide were fed into the system for 6 hours under stirring, and then stirred at 165°C for 1.5 hours. After cooling, toluene was supplied to the system so that the solid content was adjusted to 22% by mass.

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

<Synthesis example 2> Synthesis of radical polymer with hydroxyl 2.3 kg of styrene/ethylene/propylene/styrene copolymer was added to 10L of toluene, the temperature was raised to 112°C in a nitrogen environment, and 4L of toluene was distilled out. After the temperature was raised to 165°C, 265 g of 2-hydroxypropyl acrylate and 74 g of di-tert-butyl peroxide were fed into the system for 5 hours under stirring, and then stirred at 165°C for 2 hours. After cooling, toluene was supplied to the system so that the solid content was adjusted to 18% by mass.

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

<Synthesis example 3> Synthesis of radical polymer without hydroxyl 3 kg of the propylene/1-butene copolymer was added to 10 L of toluene, and the temperature was raised to 145° C. in a nitrogen environment to dissolve the copolymer in toluene. Furthermore, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system under stirring for 4 hours, and then stirred at 145°C for 2 hours. After cooling, put in a large amount of acetone to precipitate the modified copolymer, filtered and washed with acetone, and then vacuum dried. The mixed solution of toluene and MEK was supplied to the system to adjust the obtained polymer to a solid content of 10% by mass.

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

[Material] In the examples and comparative examples, the raw materials used when preparing the composition (coating material) and the substrate used when coating the composition are as follows.

＜Alkyl etherified amino resin (A)＞ (A-1) Butyl etherified melamine resin: "U-VAN 520" (manufactured by Mitsui Chemicals Co., Ltd.) ‧Solid content: 85% by mass ‧Weight average molecular weight: 1,800 ‧SP value: 9.2 (A-2) Butyl etherified melamine resin: "U-VAN 20SB" (manufactured by Mitsui Chemicals Co., Ltd.) ‧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: "U-VAN 225" (manufactured by Mitsui Chemicals Co., Ltd.) ‧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 ＜Free radical polymer with hydroxyl group (B)＞ (B-1) Free 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 ＜Free radical polymer with hydroxyl group (B)＞ (B-2) Free 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) Hydride of 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 ‧Hydroxy Value: 73mgKOH/g ‧SP value: 8.6 <Free 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) Hydroxyl-free butadiene polymer "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) "P-toluenesulfonic acid monohydrate" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ＜Surface adjuster (D)＞ (D-1) Fluorinated surface conditioner "SURFLON IF-HC125" (manufactured by AGC SEMI CHEMICAL) (D-2) Fluorinated surface conditioner "SURFLON S-242" (manufactured by AGC SEMI CHEMICAL) (D-3) Polysiloxane-based surface conditioner "BYK-3560" (manufactured by BYK Co., Ltd.) (D-4) Sulfonic acid-based surface conditioner "PELEX TR" (manufactured by Kao Co., Ltd.) ＜Substrate＞ ‧Biaxially stretched polypropylene film (210mm×297mm×thickness 50μm) [Evaluation items and evaluation methods] The evaluation of the coating film (cured film) produced in the Examples and Comparative Examples was performed as follows.

＜Appearance of coating film＞ The haze of the cured film just after curing was measured with a haze meter (Model NDH-4000, manufactured by Nippon Denshoku Industries Co., Ltd.). In addition, the test piece in which the resin composition was cured was visually evaluated based on the following criteria. A: No foreign matter, whitening, or abnormal appearance (○) occurs. B: Foreign matter or bleaching, with abnormal appearance (╳).

＜Tackiness＞ According to JIS K5400 8.5.2: 1990, use a knife on the coating film (hardened film) and draw a checkerboard with a width of 1 mm in the vertical and horizontal directions according to the way to the substrate, and then stick the cellophane tape on its surface. , Evaluate the state of the coating film after instant peeling according to the following criteria. A: No peeling or coating film defects (○). B: Peeling and coating film defects (△) occurred partially. C: Peeling and coating film defects (╳) appear across the board.

＜Scratch resistance＞ After wiping the cured film immediately after curing with steel wool (BONSTAR No. 0000, manufactured by Japan Steel Wool Industry Co., Ltd.), the state of the coating film (cured film) was evaluated according to the following criteria. A: The number of scars is 0 to 5 (○). B: The number of scars is 6 to 10 (△). C: The number of scars is 11 or more (╳).

＜Printing suitability＞ Measure the adhesiveness of the ink (copolymer of vinyl acetate and vinyl chloride) printed on the cured film and the contact angle of the cured film with water. In addition, the adhesion of the ink was evaluated in accordance with JIS K5400 8.5.2:1990. The contact angle of water is measured in accordance with JIS R3257: 1999 "Test method for wettability of substrate glass surface". Then, the printing suitability was evaluated based on the following criteria. A: The contact angle of water is 89∘ or less, and there is no peeling or defect of ink (◎). B: The contact angle of water is more than 90∘, and there is no peeling or defect of ink (○). C: The contact angle of water is 89∘ or less, and there are some peeling and defects of ink (△). D: The contact angle of water is above 90∘, and there are some peeling and defects of ink (△). E: The contact angle of water is 89∘ or less, and there are ink peeling and defects (╳) across the board. F: The contact angle of water is above 90∘, and there are ink peeling and defects (╳) across the board.

[Example 1] Prepare 20.2g of amino resin solution (A-1), 52.0g of radical polymer solution (B-1), add 22.2g of toluene/MEK=50/50 mixed solvent and fully dissolve and mix. Next, add 5.7 g of a solution containing 25% solid content of the acid catalyst (C-1) by PGM (with respect to 100 parts by mass of the total of the amino resin (A-1) and the radical polymer (B-1) (5 parts by mass), to prepare a thermosetting resin composition having a non-volatile content of 30% by mass. The obtained composition was coated on an OPP film with a film thickness of 50 μm using a bar coater #14, and heated with a warm air dryer under the conditions of 120 seconds and 1 minute to form a cured film with a film thickness of about 3 μm, and various tests were performed. The results are shown in Table 1.

[Examples 2~6, 11~13, Comparative Examples 1~6] The thermosetting resin composition was prepared in the same manner as in Example 1, except that it was replaced with the composition shown in Table 1 to Table 3. The results of various tests are shown in Tables 1 to 3.

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

[Example 8] Except that the radical polymer solution (B-1) is changed to the radical polymer solution (B-2), and 0.5 parts by mass of the surface modifier (D-2) is added to the thermosetting resin composition, the rest is implemented In Example 3, a thermosetting resin composition was prepared in the same manner. Table 2 shows the results of various tests.

[Example 9] Except that the radical polymer solution (B-1) is changed to the radical polymer solution (B-3), and 0.5 parts by mass of the surface modifier (D-3) is added to the thermosetting resin composition, the rest is implemented In Example 3, a thermosetting resin composition was prepared in the same manner. Table 2 shows the results of various tests.

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

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

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

[Table 1] Composition [mass parts] SP value Example 1 2 3 4 5 6 Alkyl etherified amino resin (A) A-1 9.2 60 70 80 95 — 80 A-2 9.3 — — — — 80 — Amino resins other than (A) (A') A'-1 10.2 — — — — — — A'-2 13.8 — — — — — — Free radical polymer with hydroxyl (B) B-1 8.8 40 30 20 5 — — B-2 8.9 — — — — 20 — B-3 8.6 — — — — — 20 Free radical polymer other than (B) (B) B'-1 — — — — — — — B'-2 — — — — — — — Acid catalyst (C) C-1 — 5 5 5 5 5 5 Surface conditioner (D) D-1 — — — — — — — D-2 — — — — — — — D-3 — — — — — — — D-4 — — — — — — — The total mass of (A) and (A') 60 70 80 95 80 80 (B), (B') total mass parts 40 30 20 5 20 20 Film performance Tightness A A A B A A Appearance of coating film A A A A A A Scratch resistance B A A A A A Haze of coating film (%) 1.8 1.9 1.8 1.7 1.9 1.8 Printing suitability D D D D D D Contact angle (∘) 85 83 84 83 84 82

[Table 2] Composition [mass parts] SP value Example 7 8 9 10 11 12 13 14 15 Alkyl etherified amino resin (A) A-1 9.2 80 80 80 80 40 20 — 20 — A-2 9.3 — — — — — — 10 — 10 Amino resins other than (A) (A') A'-1 10.2 — — — — — — — — — A'-2 13.8 — — — — — — — — — Free radical polymer with hydroxyl (B) B-1 8.8 20 — — — 60 80 90 80 90 B-2 8.9 — 20 — — — — — — — B-3 8.6 — — 20 20 — — — — — Free radical polymer other than (B) (B) B'-1 — — — — — — — — — — B'-2 — — — — — — — — — — Acid catalyst (C) C-1 — 5 5 5 5 5 5 5 5 5 Surface conditioner (D) D-1 — 0.5 — — — — — — 0.5 — D-2 — — 0.5 — — — — — — 0.5 D-3 — — — 0.5 — — — — — — D-4 — — — — 0.5 — — — — — The total mass of (A) and (A') 80 80 80 80 40 20 10 20 10 (B), (B') total mass parts 20 20 20 20 60 80 90 80 90 Film performance Tightness A A A A A A A A A Appearance of coating film A A A A A A A A A Scratch resistance A A A A B B B B B Haze of coating film (%) 1.8 1.7 1.8 1.8 1.8 1.8 1.8 1.8 1.8 Printing suitability C C D D B B B A A Contact angle (∘) 36 49 82 82 93 92 91 30 37

[table 3] Composition [mass parts] SP value Comparative example 1 2 3 4 5 6 Alkyl etherified amino resin (A) A-1 9.2 100 — — 80 80 — A-2 9.3 — — — — — — Amino resins other than (A) (A') A'-1 10.2 — 80 — — — — A'-2 13.8 — — 80 — — — Free radical polymer with hydroxyl (B) B-1 8.8 — 20 20 — — 100 B-2 8.9 — — — — — — B-3 8.6 — — — — — — Free radical polymer other than (B) (B) B'-1 — — — — 20 — — B'-2 — — — — — 20 — Acid catalyst (C) C-1 — 5 5 5 5 5 — Surface conditioner (D) D-1 — — — — — — — D-2 — — — — — — — D-3 — — — — — — — D-4 — — — — — — — The total mass of (A) and (A') 100 80 80 80 80 0 (B), (B') total mass parts 0 20 20 20 20 100 Film performance Tightness C C C C C C Appearance of coating film A B B B B A Scratch resistance A B B B B C Haze of coating film (%) 1.8 35.7 36.2 33.8 30.5 1.9 Printing suitability E F F E E B Contact angle (∘) 84 90 90 84 84 91 Furthermore, the above-mentioned invention is provided in accordance with the exemplary embodiment of the present invention, but this is only an example and is not a limiting interpretation. Those with ordinary knowledge in the technical field to which the present invention pertains should know that the modified examples of the present invention are included in the scope of the following patent applications. (Industrial availability)

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

1: Product label 2: Substrate 2A: Adhesion area 2B: Non-adhesive area 3: coating layer 4: Printing layer 11.11A: Adhesive labels 12.12A: Roll label

Fig. 1 is a side cross-sectional view of a label for a commodity according to an embodiment of the label of the present invention. Figure 2A is a bottom view of one embodiment of the label for goods shown in Figure 1 (the state where the adhesive area is located in the center); Figure 2B is another embodiment of the label for goods shown in Figure 1 (the state where the adhesive area is at the end) ) Bottom view.

1: Product label

2: Substrate

3: coating layer

4: Printing layer

Claims (16)

A thermosetting resin composition containing (A) Alkyl etherified amino resin with solubility parameter δ (SP value) below 10.0, (B) Free radical polymer with hydroxyl group, and (C) Acid catalyst. The thermosetting resin composition of claim 1, 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 thermosetting resin composition according to claim 1, wherein the mass ratio of the alkyl etherified amino resin to the radical polymer is 1/99 to 49/51. The thermosetting resin composition according to any one of claims 1 to 3, wherein the alkyl etherified amino resin is a butyl etherified melamine resin. The thermosetting resin composition according to any one of claims 1 to 4, wherein the hydroxyl value of the radical polymer is 20 to 200 mgKOH/g. The thermosetting resin composition according to any one of claims 1 to 5, wherein the solubility parameter δ (SP value) of the radical polymer is 8.0 to 9.0. The thermosetting resin composition according to any one of claims 1 to 6, wherein the reaction product of a radical polymer having no hydroxyl group in the above-mentioned radical polymerization system and a monomer having a hydroxyl group, The above-mentioned radical polymer without hydroxyl group is selected from the group consisting of polymers of olefins with 2 to 20 carbon atoms, polymers of olefins with multiple double bonds, and copolymers of olefins and other radical polymerizable monomers. At least one polymer. The thermosetting resin composition according to any one of claims 1 to 7, wherein the acid catalyst is p-toluenesulfonic acid. The thermosetting resin composition according to any one of claims 1 to 8, which further contains 0.1-30 parts by mass relative to 100 parts by mass of the total of the alkyl etherified amino resin and the radical polymer (D) Fluorine-containing surface regulator. A coating material for printing containing the thermosetting resin composition according to any one of claims 1 to 9. A cured product comprising the thermosetting resin composition according to any one of claims 1 to 9. Such as the hardened object of claim 11, where the contact angle of water is 20~89∘. A laminate in which a substrate, a cured film, and a printing layer have been laminated in this order, and the cured film contains the cured product of Claim 11. The laminate according to claim 13, wherein the base material comprises an olefin polymer. A label containing a layered body of claim 13 or 14, The substrate includes an adhesive area and a non-adhesive area. A method for manufacturing a laminate, which includes, after the step of applying the thermosetting resin composition of any one of claims 1 to 9 to a substrate, The step of heating the above-mentioned thermosetting resin composition to 60 to 160° C. to harden and form a cured film.

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