JPH02255824A - Thermosetting covering sheet - Google Patents

Abstract

PURPOSE:To obtain a thermosetting covering sheet having good malleability, ductility and flexibility before being cured and capable of forming a film of a high hardness after being cured, which is an uncured sheet based on a composition comprising a specified reactive acrylic resin, a blocked isocyanate, a thermoplastic resin and/or a specified reactive acrylic oligomer. CONSTITUTION:An uncured thermosetting covering sheet formed from a thermosetting resin composition mainly comprising a normally solid reactive acrylic resin having a weight-average MW of 100000-1000000, a blocked isocyanate and a normally solid thermoplastic resin and/or a reactive acrylic oligomer of a weight-average MW of 1000-10000. The above composition may further contain at least one crosslinking agent selected from among a nonblocked isocyanate, a melamine compound and an epoxy compound.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a coating that is applied to the surface of furniture, steel plates, etc. for preservation, decoration, display, etc. and is then heat-cured. This relates to sheets for use.

(Prior Art) Paint is generally used to decorate or display the surfaces of furniture, steel plates, etc.

However, when a solvent-based paint is used, the organic solvent evaporates during the work, making the work environment hasty and posing an environmental health problem. When using a water-based paint, the working environment is not affected, but there are problems such as the paint taking time becomes longer and a large amount of energy is required to dry the paint.

In order to solve these problems, sheet-like coating materials have recently been proposed to replace PR. For example, a sheet-like coating material mainly made of polyvinyl chloride has been proposed.

This coating material is applied to the surface of the A% wire board ◆, and when using such a coating material,
There is no contamination to the working environment or health and safety problems, and there is no need to dry the adhesive afterwards, which has the advantage of simplifying the work.

However, since the main component of the material is soft polyvinyl chloride, the resulting coating has poor abrasion resistance and is prone to cracking.

As an alternative to these soft polyvinyl chloride sheet materials, heat or photo-curable sheet materials have been proposed. This sheet material can be applied to the surface of an article by heating or irradiating it with light.
It hardens to form a hard film. For example, Japanese Patent Publication No. 57-13425 discloses a thermosetting composite sheet having a two-layer structure in which a layer containing a reactive unsaturated polymer, an oligomer, and a monomer, and a layer containing a radical reaction initiator are laminated. is disclosed.

(Problem to be Solved by the Invention) However, the composite sheet disclosed in the above publication contains a component that causes a polymerization reaction and a reaction initiator in different layers, so it hardens uniformly when heated and pressurized. In order to carry out the reaction, it is necessary to bring both shoulders into uniform contact, making it difficult to control heating and pressure during curing, making it impossible to obtain a uniformly cured film. Furthermore, paper% woven fabric is used as a sheet-like base material impregnated with the radical reaction initiator.

Because non-woven fabric is used, when coating the surface of an article with uneven or curved surfaces with a composite sheet, it is difficult to apply the composite sheet while stretching (17), and there are disadvantages such as not being able to obtain a good cured film. .

The present invention is intended to solve the above-mentioned conventional drawbacks, and its purpose is to have good spreadability and flexibility before hardening. We have developed a thermosetting coating sheet that can be coated well even on the surfaces of articles with uneven or curved surfaces, and can form a uniform coating with excellent impact resistance (and high hardness) after curing. It is about providing.

(#! Means for Solving the Problem) The thermosetting coating sheet of the present invention is a thermosetting coating sheet in an uncured state formed by troweling a thermosetting resin composition, and comprising: The thermosetting resin composition has a weight average molecular weight of 100.000 to 1. A reactive acrylic resin that is Oo o, o o o and is solid at room temperature, block incyanate, and a thermoplastic resin and/or mj that is solid at room temperature.
l average molecular weight is 1°000~10. It is characterized by containing a reactive acrylic oligomer which is OOO as a main component, thereby achieving the above object.

The present invention will be explained in detail below.

The thermosetting coating sheet of the present invention is an uncured thermosetting coating sheet formed from a thermosetting resin composition. For example, the following three are listed.

■ Weight average molecular weight is 100.000~1.000゜0
00 and whose main components are a reactive acrylic resin that is solid at room temperature, block incyanate, and a thermoplastic resin that is solid at room temperature.

■ Weight average molecular weight is i o o, o o o~i,
o o o.

000 and is solid at room temperature, a blocked isocyanate, and a weight average molecular weight of i, o.
A reactive acrylic handle that is a reaction OO of o~10.000 and is solid at room temperature, a blocked isocyanate, a thermoplastic resin that is solid at room temperature, and a weight average molecular weight of 1
The main component is a reactive acrylic oligomer with a molecular weight of 10,000 to 10,000.

The reactive acrylic handle is an acrylic polymer having multiple hydroxyl groups, amino groups, and/or carboxyl groups, and is a solid polymer at room temperature (25° C.). Such reactive acrylics include, for example, (meth)acrylic acid ester monomers, styrene derivative monomers, 2-t
: A (meth)acrylic acid ester monomer having a hydroxyl group such as droxyethyl (meth)acrylate A (meth)acrylic acid ester monomer having an amine 7 group such as 2-aminoethyl (meth)acrylate and/or (
It can be obtained by copolymerizing a hexamer having a carboxyl group such as meth)acrylic acid. The Xt average molecular weight of the reactive acrylic resin can be changed to y depending on the conditions when performing a polymerization reaction using an initiator, and the reactive acrylic resin used in the present invention has a weight average molecular weight of i o The range from o, o o o to 1,000.000 is selected. Weight average molecular weight is 100,000
If it is less than 20%, it becomes difficult for the obtained thermosetting coating sheet to maintain its sheet shape. Therefore, for example, sufficient elongation cannot be obtained when pasting is applied during stretching during work.

In some cases, cracks or cracks may occur. If the weight average molecular weight exceeds LOO, 000, the resin composition mixed with block incyanate etc. will have poor moldability and will be difficult to produce into a covering sheet.

The above block inocyanate is a reactive acrylic resin (
When a reactive acrylic oligomer is blended, it is used as a heat-reactive curing agent to cure the reactive acrylic resin and the reactive acrylic oligomer. Here, blocked incyanate refers to a compound in which the incyanate group of an incyanate compound having two or more incyanate groups in the molecule is blocked with a blocking agent such as phenol, ogisime, ε-caglolactam, or malonic acid ester. means. Examples of the above incyanate compounds include monomers such as tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, inphorone diisocyanate, trimethylolglopan adducts, incyanurate modified products, carbodiimide modified products, etc. be. In block inocyanate, the above-mentioned blocking agent is removed by heating.

The resulting incyanate group causes a crosslinking reaction with the hydroxyl group, amino group, or carboxyl group of the reactive acrylic resin (reactive acrylic resin and reactive acrylic oligomer when a reactive acrylic oligomer is blended).

The content of blocked isocyanates is determined by the amount of hydroxyl groups, amino groups, or carboxyl groups contained in the reactive acrylic resin (in the case where a reactive acrylic oligomer is blended, the reactive acrylic resin and the reactive acrylic oligomer), It is preferable to adjust the ratio to the incyanate group contained in the blocked isocyanate in a range of 0.5 to L5, more preferably in a range of 0.8 to L2.

The above thermoplastic resin is a solid resin at room temperature (25°C), and this thermoplastic 5jlf&% improves the flexibility of the thermosetting coating sheet and prevents the occurrence of cracks etc. when handling the sheet. It is used to reduce the amount of water and improve handling. As the thermoplastic resin, those having good compatibility with the reactive acrylic resin, such as acrylic, melliester, polyvinylidene heptadide, styrene, and polyvinyl chloride resins, are preferably used.

The above thermoplastic resin has a solid content of 10% of reactive acrylic resin.
It is preferably added in an amount of 1 to 30 parts by weight, more preferably 5 to 20 parts by weight, per part of 01ifi. If the amount of thermoplastic resin added is less than the IM part (F), the flexibility cannot be improved much, and if the amount added is more than the 30°C foot part, the sheet's ductility and hardness will deteriorate.

The above-mentioned reactive acrylic oligomer, like the above-mentioned thermoplastic resin, is used to improve the flexibility of the thermosetting coating sheet and improve the handling properties of the sheet. This reactive acrylic oligomer is the reactive acrylic St
The polymer is an acrylic polymer having multiple hydroxyl groups, amino groups, or carboxyl groups, and is preferably a solid or solid solution polymer at room temperature. Such reactive acrylic oligomers include, for example, (meth)acrylic acid ester monomers, methane derivative monomers, and (meth)acrylic acid ester monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate. - It is obtained by copolymerizing a (meth)acrylic acid ester having an amino group such as aminoethyl (meth)acrylate or/and a heptamine having a carboxyl group such as (meth)acrylic acid.

This reactive acrylic oligomer mainly consists of acrylate repeating units, with hydroxyl groups and amine 7
An oligomer having a group or/and a carboxyl group and having a weight average molecular weight of 1,000 to 10,000 is used.

The weight average molecular weight of the reactive acrylic oligomer is 1.00
If it is less than 0, the flexibility of the obtained thermosetting coating sheet will deteriorate, and it will be easy to crack or crack during application. Conversely, if the weight average molecular weight exceeds 10,000, the plasticizing effect cannot be achieved. In addition, reactive acrylic oligo
is preferably added in an amount of 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the solid content of the reactive acrylic resin. The amount of oligomer added is 1
If the amount is less than 1 part by weight, the thermosetting coating sheet will have poor flexibility. On the other hand, if the amount of oligomer added is 1 oz.
When the amount exceeds 1 part by weight, the viscosity decreases and fluidity increases, making it difficult to maintain the sheet shape.

The above-mentioned reactive acrylic oligomer and thermoplastic resin may be used alone or in combination. In addition, the thermosetting resin composition may contain fillers, rust preventives,
Anti-aging agents, colorants, etc. may also be contained.

In addition, the thermosetting N resin composition may further contain at least one crosslinking agent selected from the group consisting of unblocked incyanate, melamine crosslinking agent, and epoxy crosslinking agent, The thermosetting coating sheet obtained from this composition has a semi-cured state due to the fact that the crosslinking agent reacts with some of the functional groups of the reactive acrylic resin at room temperature. After attaching this sheet to the item,
By heating to the reaction temperature of block incyanate, reactive acrylic S in the sheet! The sheet can be completely cured by reacting the functional groups of the fat with the incyanate groups of the blocked isocyanate. In this way, by using a sheet in a semi-cured state, the sheet is further given malleability and flexibility and is free from cracks during processing.

It is possible to prevent cracking, etc., and to impart flatness to improve the appearance after curing.

The above-mentioned unblocked incyanate is an incyanate compound having two or more incyanate groups in the molecule, such as tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, toridine diincyanate, triphenylmethane triincyanate. , tris (methyl incyanate)
Thio 7 male 7 ite% P-phenylene diisocyanate, xylylene diisocyanate, bis(incyanate methyl) cyclohexane, dicyclohexylmethane diincyanate, bis(incyanate methyl) cyclohexane, hexypmethylene diisocyanate, lysine diisocyanate, trimethyl 7 \ Monovolumes such as xamethylene diincyanate and inphoron diincyanate, or trimethylol gulonobiliary adducts of these monovolumes,
Examples include insiaslate modified products, biscret modified products, carbodiimide modified products, fletane modified products, allophanate modified products, and the like.

The amount of incyanate added varies depending on the sheet forming method, but it is
The NCO has a functional group value: NCO=l:α01-0.9
The amount is preferable.

The above melamine crosslinking agents include melamine, urea, thiourea, guanidine, guanamine, acetoguanamine,
Trimethylol melamine, hexamethylol melamine, dimethylol urea, dimethylol guanidine, dimethylol acetoguanidine, dimethylol benjibuandine, etc., which are made by reacting formaldehyde with a material having a polyfunctional 1-mino group such as benzoguanamine or dicyandiamide, are mixed with butyl alcohol. It is etherified melamine resin that has been reacted with an alcohol such as melamine or probyl alcohol.

The amount of these melamine-based crosslinking agents added does not have a fixed value because the functional groups of the reactive acrylic resin are sealed like incyanate, so when adding them, the amount to be added is determined by conducting preliminary experiments before sheet creation. For example, functional group value: OR (ether value) = 1:0. The foot of the mountain from 1 to L2 is preferable.

The above-mentioned epoxy crosslinking agent is a glycidyl compound of polyhydric alcohol, and is used together with a Lewis acid catalyst. For example, glycidyl compounds such as butadiene dioxide, hexacine dioxide, triglycidyl ether amine of heptatalic acid, diglycidyl ether of aniline, tetraglycidyl ether of phenylene diamine, dicrycidyl ether of sulfonamide, triglycidyl ether of glycerin, etc. polyether modified diglycidyl,
Examples include polyester-modified diglycidyl compounds and fletane-modified diglycidyl compounds (polymers).

The amount of this epoxy crosslinking agent added is based on the functional group value.
Functional group: CIIICH, O (epoxy group) = 1:
0. The amount of O1 to 0.9 is preferable. In addition, since this epoxy crosslinking agent reacts with functional groups to generate OH groups, the amount of blocked incyanate added at the same time is determined by the equivalent amount of the remaining functional groups of the reactive acrylic resin and the hydroxyl groups generated. It is preferable to add about 30 to 80% of the total amount.

The amount of the crosslinking agent added is preferably within the range mentioned above, but in reality, depending on the reactivity of the reactive acrylic resin used, reactions between crosslinking agents, such as reactions between melamine crosslinking agents and epoxy crosslinking agents, Since reactions between the reactants and the functional groups of the reactive acrylic resin occur, the actual addition ff
1e If you get stuck, be careful! ! It is preferable to make a decision after conducting experiments.

The thermosetting coating sheet of the present invention can be either an uncured sheet in which the functional groups of the acrylic resin contained in the composition have not reacted, or a semi-cured sheet in which -S has been reacted with the acrylic resin. It can be used as a sheet.

When used as a semi-cured sheet, this can be done by heating the block incyanate to the reaction temperature for a predetermined period of time, or by adding the above-mentioned crosslinking agent.

In the semi-cured base sheet, it is preferable that 0.01% to 80% of the total number of functional groups of the reactive acrylic resin contained in the sheet be reacted. That is, the reaction rate (initial curing rate) of this functional group differs depending on how the sheet is used. For example, if the adherend to be pasted has convex or vertical parts, or if the sheet is being applied at a fairly high temperature (30°C or higher), the sheet should be made to elongate by more than 100% at the sheet forming temperature. , α0X-40%, more preferably 1 to 30% of the functional groups are crosslinked with isocyanate. In addition, when the covering sheet is used in places where high pressure is applied to the sheet, such as press molding or insert injection molding, 20 to 80% of the functional groups are reacted to withstand the molding temperature and resin pressure. It is better to use what you have. The appropriate range of the reaction rate of these functional groups may vary somewhat depending on the molding temperature.

The film thickness of the thermosetting sheet of the present invention varies depending on the nature of the attachment of the sheet to the adherend and the function imparted to the adherend.
Considering the case of pasting on an uneven adherend surface, 2
The thickness is preferably about 0 to 5()0 μm, but when attached to a flat surface, the thickness may be 5 to L000 μmN degrees.

As the coloring agent, pigments, dyes, etc. used in ordinary painting can be used. For example, pigments include titanium oxide, iron oxide, carbon black, cyanine pigments, and quinacridone pigments, and dyes include azo dyes, anthraquinone dyes, indigoid dyes, and stilbene dyes.
Further, metal powders such as aluminum 7 lake, nickel powder, gold powder% silver powder, etc. may be added. When using a coloring agent with high molar properties, the total amount of colorant should be 100 parts by weight of resin solids and 1%
Preferably.

A thermosetting resin composition is obtained by mixing the above components, and a thermosetting coating sheet is formed from this heat-sandable resin composition.

The thermosetting coating sheet constructed in this manner may be manufactured by any method. For example, a reactive acrylic resin, a blocked incyanate, a reactive acrylic oligomer and/or a thermoplastic resin, and a suitable organic solvent are mixed.

The above reactive acrylic resin and reactive acrylic oligo! −
is often commercially available as an organic solvent solution, so
In that case, there is no particular need to add an organic solvent. Next, the mixture thus obtained was coated onto a #C111 film that had been subjected to a release treatment using a silicone II molding agent, and then heated and dried. is obtained.

If the thermosetting sheet for branch rods obtained in this manner does not have sufficient adhesion to the article to be coated, as shown in FIG. An adhesive layer 2 may be provided, and by attaching the sheet 1 to the surface of the article via this adhesive layer 2, it is possible to improve the adhesion between the cured hard coating and the article. As the adhesive forming the adhesive layer 2, pressure-sensitive adhesives, hot-melt adhesives, post-curing adhesives, and the like are preferably used. Mixtures and laminates of these adhesives can also be used. -) It was. The adhesive layer 2 may be formed by sequentially laminating a plurality of different types of adhesives.

Among the above adhesives, pressure-sensitive adhesives include rubber-based, acrylic-based, phrethane-based, and silicone-based adhesives. Examples of hot-melt adhesives include adhesives such as ethylene-vinyl acetate copolymer, monomer M, styrene-isoprene-styrene block copolymer system, and acrylic adhesive. The post-curing adhesive layer includes, for example, a microcapsule-curing adhesive, and its materials include, for example, uncrosslinked unsaturated polyester adhesives, self-crosslinking acrylic adhesives, etc. Ru. The thickness of the adhesive layer is generally preferably 30 to 100 μm.

Any method may be used for laminating the adhesive layer 2. For example, the thermosetting coating sheet 1 is formed on a releasable base material by the method described above, and then the fg containing adhesive is formed. True liquid! An adhesive layer 2 is formed by applying it to the wheat surface of the Il-type base material and drying it by heating, and the thus obtained thermosetting covering sheet 1 and the adhesive layer 2 are laminated, and then, For example, a thermosetting coating sheet with an adhesive layer can be obtained by applying pressure with a roll press to press the two together, and then removing the releasable base material.

When the resin composition constituting the thermosetting coating sheet 1 has a low viscosity, the sheet 1 becomes an inner cone that maintains its shape.

In such a case, as shown in FIG. 2, the shape retention of the sheet 1 can be improved by providing the support layer 3 on the sheet 1. Furthermore, %5s as shown in Figure 3
The adhesive layer 2 may be provided on one surface of the sheet 1, and the support layer 3 may be provided on the other surface of the sheet 1. The support layer 3 is used to maintain the shape of the entire thermosetting sheet 1, and with this support layer 3 attached, the sheet 1 is attached to the surface of an article having a three-dimensional curved surface.
In order to impart flexibility to this support-3 and ensure desired ductility, it is heated as necessary. After the thermosetting coating sheet 1 is applied to the article 1c and cured, the support layer 3 may be peeled off and removed.

The support layer 3 is a film that is extensible at least under heating (for example, a thermoplastic I# resin film or a rubber film).
Preferably, it consists of:

Examples of the thermoplastic resin constituting the film include soft polyvinyl chloride, polyurethane, acrylic resin, polyester, ethylene-vinyl acetate copolymer, polyethylene, and polyglopylene. Examples of materials for the rubber film include natural rubber, styrene-butadiene rubber, nitrile-butadiene rubber, imprene rubber, butadiene rubber, talolobrene rubber, cretan rubber,
Examples include silicone rubber and acrylic rubber. A mixture of these thermoplastic S1 fats and rubbers can also be used,
Alternatively, the support layer 3 can be formed by laminating these layers. A thermoplastic camphor resin film often exhibits ductility under heating, but if a rubber film is used, ductility can be obtained at room temperature.

The support layer 3 may be laminated on the thermosetting covering sheet 1 in advance, and after forming the thermosetting covering sheet 1, the supporting layer 3 may be laminated on the supporting layer 114.
The thermoplastic resin film or rubber film constituting No. 3 may be laminated. The thickness of the support layer 3 is usually 10 to 50
0 μm is preferable.

The thermosetting coating sheet of the present invention can be used, for example, as follows to form a hard coating on the surface of an article. As described above, since the thermosetting coating sheet has a certain degree of flexibility at room temperature, it is stretched without heating and attached along the surface of the article. Next, at least the part of the article to which the thermosetting coating sheet has been applied is heated to a temperature higher than the decomposition temperature of the block incyanate contained in the sheet, and a reactive acrylic resin (if a reactive acrylic oligomer is contained, this is done). (reactive acrylic resin and reactive acrylic oligomer) to completely cure the sheet. In this way, a hard coating is formed on the surface of the article.

Alternatively, the sheet may be cured at the same time as the thermosetting coating sheet is applied to the surface of the article by hot pressing using a mold that fits the article. According to this method, even articles having uneven surfaces can be easily coated with a sheet. If the above-mentioned thermosetting coating sheet has poor adhesion to the article to be coated, use a sheet with an adhesive layer as described above to ensure sufficient adhesion to the article. can get. In addition, when the resin composition constituting the thermosetting coating sheet is in the form of a solid solution, by using a sheet having a support layer, the sheet can be attached to the surface of the article, and when heated, This prevents the shape of the sheet from deforming more than necessary. The pasting of the sheet with the support layer is sometimes heated, if necessary, in order to impart flexibility to the support M and ensure the desired spreadability. Attach a thermosetting coating sheet to the article,
After heating and curing, the support layer may be peeled off and removed.

(Example) The present invention will be explained in detail below based on examples.

Example 1 Acrylic polyol (manufactured by Nippon Shokubai ■, Arotan 2040
-145 Glass transition temperature 40℃, heavy gourd average molecular weight 33
9.000, solid content of OHHBO2 1001 parts (hereinafter referred to as parts), made by acrylic polyol oligoide ■, dicaride H870: Gax transition point -45°C
, weight average molecular JIL2200-2500, OH number 2
00) in solid content and 30 parts of blocked incyanate (
Manufactured by Narita Pharmaceutical Co., Ltd., Kugne b B 8 1 5 N
: Oxime form of hydrogenated diphenylmethane diincyanate. 86 parts (containing 10 equivalents of incyanate groups based on the acrylic polyol and ataryl polyol oligomer hydroxyl groups) of NGO% 7.3) were mixed with stirring while stirring.

This mixture was applied to the surface of the 1111 mold of a polyethylene terephthalate film (manufactured by Soken Kadama #!@, film thickness: 50 fitta) that had been released using a silicone release agent so that the film thickness after drying would be 100 μm. The film was dried at 80° C. for 5 minutes, and then the film was peeled off to obtain a thermosetting coating sheet for uncured dairy. The thickness of the obtained thermosetting coating sheet was about 50 pm.

The thermosetting coating sheet thus obtained was subjected to a tensile test, a bond test, and its hardness was measured.

For the tensile test, a rectangular test piece (20×l OOmr ) was cut from the thermosetting coating sheet2, and the test piece was stretched 100% in the length direction under atmospheric conditions of room temperature and 80°C. It was investigated whether the sheet r was cracked or cracked.

As a result, even at 100% elongation P, no cracking or cracking occurred.

The coating test was conducted using a steel plate curved into a convex lens shape (curvature radius 50
(1!II+, diameter of the bottom is 30mm), coat the convex surface with a thermosetting sheet (20x20 side) at 80＠C
It was vacuum formed. As a result of No. 7, it was possible to coat the sheet well without causing wrinkles. Next, this coated steel plate was heated at 1i) 0°C for 30 minutes to harden the acrylic polyol and acrylic polyol oligo to form a strong coating (WIl, approximately 40 μm).
) was obtained. The hardness was measured by a pencil hardness test according to JIS K54001m. As a result, the hardness was H.

Example 2 Acrylic polyol (manufactured by Nippon Shokubai ■, Arokun 2040)
-140 Ni glass transition temperature 20℃, it average molecule t36
9,000.0Hflli120) in solid content, 100 parts in solid content, acrylic polyol oligomer (manufactured by Nippon Carbide ■, Nikalide H470, glass transition point -37°C, weight average molecular @ 2200 to 2500, OH number 2oo) fa: 30 in solid content and block incyanate (manufactured by Narita Pharmaceutical Co., Ltd., Takenate B815N) in a solid content of 111 parts (
The above acrylic polyols and acrylic polyol oligos! A thermosetting coating sheet was obtained in the same manner as in Example 1, except that a sheet having an incyanate group equivalent to LO for the hydroxyl group of - was used.

The obtained thermosetting coating sheet was tested in the same manner as in Example 1. As a result, the tensile IA test.

No cracks or cracks occurred during electrolytic corrosion and stretching at 80°C.

In the coating test, the convex surface was coated well without wrinkles. The pencil hardness of the film after heat curing was H.

Comparative Example 1 Acrylic polyol (manufactured by Nippon Shokubai Co., Ltd., Arotan 2040
-144 Ni glass transition temperature 20°C, average molecular weight 104.
100 parts of acrylic polyol oligomer (manufactured by Nippon Carbide ■, Nikakuito H870 Niglass transition point ~ 20℃ 2 weight average molecular weight 2)
200 to 2500, OH value 200) in a solid content of 30 parts and blocked incyanate (manufactured by Narita Pharmaceutical Co., Ltd., Tagenate B815N) in a solid content of 86 parts (% relative to the hydroxyl groups of the above acrylic polyol and acrylic polyol oligomer). A thermosetting coating sheet was obtained in the same manner as in Example 1 except that 0 equivalent of incyanate group) was used.

The obtained thermosetting coating sheet was tested in the same manner as in Example 1. As a result, the tensile test is.

It was not possible to obtain 100% elongation at room temperature and at 80°C. In addition, in the coating test, the shape retention of the sheet shape was poor, and it was difficult to perform vacuum forming and pasting.

Comparative Example 2 00 parts and block incyanate (Narita Pharmaceutical Co., Ltd. 11 Takenate 8815N) were used in a solid content of 49 parts (having 10 equivalents of incyanate groups based on the hydroxyl groups of the above acrylic polyol). Same as Example 1 [
A thermosetting coating sheet was obtained by straining.

The obtained thermosetting coating sheet was subjected to the open fc test as in Example 1. As a result, the tensile test was performed at 80°C.
It was sealed to 0.00% elongation and showed uniform elongation without cracking or galling. It was not possible to obtain an IQO% elongation at room temperature.

In addition, in the coating test, the convex surface of the steel plate curved into a convex lens shape was successfully coated without wrinkles. The pencil hardness of the film after heat curing was 2H.

Comparative Example 3 Acrylic polyol (manufactured by Nihon Shoku #L■, Arotan 204
0-145・Glass transition temperature 40℃, average molecular weight 339
,000), solid content i00 parts, acrylic polyol (
Manufactured by Nippon Shokubai ■.

Alotane 2040-136: Glass transition temperature 40℃, average molecular weight j128,000, OHHBO2 solid content 30
% Example except that 64 parts of block incyanate (manufactured by Narita Pharmaceutical Co., Ltd., Takene B815N) was used in terms of solid content (contains incyanate groups of LO equivalent to the hydroxyl groups of the above acrylic polyol). A thermosetting coating sheet was obtained by using the same length as No. 1.

The obtained thermosetting sheet for branch stems was tested in the same manner as in Example 1. As a result, the tensile test was 10
0% elongation of 1 piece [, showing uniform elongation with no cracks or cracks. It was not possible to obtain 100% elongation at room temperature. In addition, in the coating test, the convex surface of the steel plate curved into a convex lens shape was successfully coated without any wrinkles. The pencil hardness of the film after heat curing was H.

Acrylic polyol (manufactured by Nippon Shokubai ■, Alotane 2040)
-145 Glass transition temperature 40℃, average molecule 1133
9.000), 100x parts of solid content, acrylic polyol oligomer (manufactured by Nippon Carbide ■; Kalide H)
870) in solid content, 30 parts of acrylic t# resin (Kyowa Gas Chemical I 1ll-V b"'Rabet Beads Gl
98 or EH-1000P) in the solid content as shown in Table 1, and 6ty'Il (the above acrylic The pyriol and hydroxyl groups of the acrylic polyol oligomer (as opposed to the incyanate groups of the LO) were mixed with stirring.

This mixture was applied to a polyethylene terephthalate film (manufactured by Soken Kako ■,
The film thickness after drying is l 00 on the lIl type surface with a film thickness of 40 μm.
/l m and dried at 70° C. for 1 hour to obtain a thermosetting coating sheet with a film.

Next, to examine the toughness of this sheet, we conducted a falling ball test. In the falling ball test, the film was peeled off from the film-attached thermosetting coating sheet obtained above, and the sheet was stretched over a cylinder with a diameter of 10 cm, as shown in Figure 4, and poured with a predetermined heavy liquid. When the ball was placed in the shade from the height of the scrap, the sheet was broken with a ○, and the sheet that did not break was marked with an x. In addition, f$ is a No. 16 steel ball (diameter 1
/2 inch, weight 8.35V) was used.

In addition, the above mixture was applied 7 times on a painted steel plate and heated to 70°C.
After drying for one day, heat curing at 60°C for 30 minutes,
A pencil hardness test was then conducted. The pencil hardness test was conducted on the test specimens at 25° C. and 80° C., respectively.

The results are shown in Table 1.

Table 1 Comparative Example 4 A mixture was obtained by straining in the same manner as in Example 1, except that Alotane 2040-134 (average molecular jL 9300, manufactured by Nippon Shokubai ■) having a small average molecular weight was used as the acrylic polyol. A similar test was conducted. It was difficult for the obtained thermosetting coated sheet to maintain its sheet shape.

Example 9 300 parts of ethyl acetate, reactive acrylic resin I! i1(
Methyl methacrylate, methacrylic acid and acrylic acid 2
-Aminoethyl copolymer, Mw=565.000, T
g35℃%C0OH value 40 and NH, value 40) solid content 1
00 parts, anti-16 acrylic oligomer (copolymer of methyl acrylate, 2-hydroxyethyl methacrylate, butyl acrylate, methacrylic acid, Mw = 4,0
00. Tg-10″C, OH value ioo, C0OH value 4
0), solid content 30 parts, block inocyanate (manufactured by Kurade Pharmaceutical Co., Ltd., Kukune) B-815N, hydrogenated diisocyanate; ketoxime block N C0 of methane diisocyanate
7.3%) 75 parts (this crosslinking agent is 10 parts per functional group of the reactive acrylic resin and reactive acrylic oligomer)
(containing equivalent amounts of isocyanate groups) were mixed with good stirring. This mixture was coated on the release surface of 74 lumens of polyethylene tele 7 tarley (PET) which had been completely treated with silicone M using an agelator and dried at 80° C. for 5 minutes to prepare a thermosetting sheet. The thickness of the sheet is 8011m
Next, the sheet was heated to 50'C by vacuum contact molding (vacuum packaging molding) on a hemisphere with a radius of 15 cm coated with acrylic melamine, and the degree of vacuum reached was l.
I attached it when I got OTorr P. 16 parts of it were heat-cured at 1°C for 30 minutes to form a 1° coating. The hardness of this coating was a pencil hardness, and the H1 adhesion was 100/100 in an IF width board test.

Example 1O 300 parts of ethyl acetate, reactive acrylic resin (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and ethyl acrylate, M w -250.0
00, T g l 5℃, OIH value 40 and C0OH value 2
0) to 100 parts of solid content, reactive acrylic oligomer (
20 parts of solid content (same as above) and 54 parts of blocked incyanate (same as above) (this crosslinking agent has an incyanate group of L O5 storm with respect to the functional group of the above-mentioned reactive acrylic resin and reactive acrylic oligomer). Mixed with stirring. PET treated with silicone 1lIf type of this mixture
Coat the release surface of the film with an appliguter and heat at 80℃r.
It was dried with a trowel for 5 minutes to create a thermosetting sheet. The thickness of the sheet was 100 μm.

Next, this sheet is vacuum-adhesively molded (vacuum packaging molded) on a chinaware plate with a radius of 10 (!11 height 6 and a radius of 5 cIR on the side bottom).
I attached it when it became orr. This was cured by heating at 160° C. for 30 minutes to form a coating. The hardness of this coating is HB on a pencil hardness, and the adhesion is 10 on a 1lf/1 width board test.
It was 0/100.

Example 11 A reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and aminobutyl methacrylate, Mw = 3) was added to 300 parts of ethyl acetate.
68,000, TglO ℃, OH number 40 and N Hz number 4
0) Acrylic polycarboxylic acid oligomer (copolymer of stearyl methacrylate, methacrylic acid, and butyl acrylate, M w = 5.000,
Tg -20°C, acid value 80) 20 parts solids, blocked incyanate (manufactured by Nippon Polyurethane Industries, Coronate 2)
513, ethyl acetoacetate block of incyanurate of hexamethylene diinocyanate, NGO=1α2%
) 62 parts (this crosslinking agent is %L based on the functional groups of the above-mentioned reactive acrylic resin and acrylic polycarboxylic acid oligomer)
2 equivalents of incyanate groups) were mixed with good stirring. This mixture was coated with a 1llt type surface rough applicator made of PET film treated with silicone pIi type, and dried at 70°C for 10 minutes to prepare a thermosetting sheet. The thickness of the sheet was 100 μm.

Next, this sheet was molded into a polypropylene hemisphere with a radius of 151 cm (vacuum packaging molding) at 60°C.
It was heated to 5'['orr] and was attached when the ultimate vacuum level reached 5'['orr]. A coating was prepared by heating and curing it at 120°C for 2 minutes and at 70°C for 1 hour. The hardness of this coating is B on the pencil hardness scale, and the adhesion is If1 width radix base test 00/100.
Met.

Example 12 300 parts of ethyl acetate was mixed with reactive acrylic resin (methyl methacrylate, methyl acrylate, and methacrylic #2-
Copolymer of hydroxyethyl, acrylic acid, and 4-aminoethyl methacrylate, Mw=360.000. T
g20°C, OHH2O2CoOH value 20 and NH.

40) in a solid content of 100 parts, a reactive acrylic oligomer (same as 1) in a solid content of 30 parts, and a block incyanate (same as 3) in a solid content of 72s (this crosslinking agent is the same as the above reactive acrylic resin and reactive acrylic oligomer). (having LO equivalent of incyanate group with respect to the functional group with E) were mixed with thorough stirring. This mixture was applied to the ma side of the PETy film treated with silicone IIi type using an applicator, dried at 60'C for 20 minutes, and further heated to % 160'C.
Initial curing treatment was performed for 5 minutes to create a thermosetting sheet.

The initial curing of this thermosetting sheet was determined by infrared absorption analysis (I
R) etc., 25% of the total functional groups were initially cured. The thickness of the sheet was 50 μm.

Next, this sheet was fixed in an injection mold for forming a cylindrical shape with a radius of 10 cm and a height of 6a so that the sheet was in the cutting plane with respect to the metal tM, and the boriethe-limide resin was injected and the sheet I was attached. This was heated and cast at 160° C. for 20 minutes to form a coating. The hardness of this coating is HB on the pencil hardness scale, the adhesion is 1, the width is M, and the board test is 00/100.
Met.

Example 13 A reactive acrylic resin (a copolymer of methyl methacrylate, methacrylic acid, and 2-aminoethyl acrylate, Mw = 492,000, Tg 35°C) was added to 300 parts of ethyl acetate.
%C0OH value 40 and NH, value 40) to 100 parts solids,
20% solid content of reactive acrylic oligomer (same as 1)
parts, blocked isocyanate (same as 1), 53 parts (this crosslinking agent has 0.8 parts of incyanate groups with respect to the functional groups of the above-mentioned reactive acrylic resin and reactive acrylic oligomer), epoxy crosslinking agent ( Made by CiverGeigy, Araldite CYl 75. Epoxy equivalent: 160, engineering value corresponding to the functional group value: 220) 6.6B (10% of the functional groups of the reactive acrylic resin is initially cured). Mixed with thorough stirring. . This mixture was applied with an applicator to the release surface of a polyethylene terephthalate (PET) film subjected to silicone release treatment, and dried at 80'C for 5 minutes to produce a thermosetting sheet. The thickness of the sheet is
It was 80 μm.

Next, this sheet was coated with alkyd melamine and applied to a hemisphere with a radius of 10 openings, and the sheet was heated to 6o''C by vacuum contact molding (vacuum packaging molding) to reach a vacuum level of 6 Torr.
I attached it when it arrived. This was heated and cured at 160° C. for 30 minutes to form a coating. The hardness of this coating is H on the pencil hardness scale.
The percent adhesion was 100/100 in the 11111 width board test.

Example 14 To 300 parts of ethyl acetate, a reactive acrylic resin (a copolymer of methyl methacrylate, methacrylic acid 2-hydroxyethyl acid, and acrylic acid, Mw = 250.QOO%Tg
i5℃, OX (value 40 and C00H value 40) solid content 100
11C1 reactive acrylic oligomer (copolymer of methyl acrylate, 2-amino/ethyl acrylate, acrylic acid and methyl methacrylate).

Mw=8,000. Tg l O'C, NHIH1O
6CoOH value 30) as a solid content, 55 parts of blocked incyanate (same as 1) (this crosslinking agent is used to add 10 equivalents of isocyanate groups to the functional groups of the reactive acrylic 41 and the reactive acrylic oligomer). ) and incyanate (manufactured by Nippon Mericletan Kogyo Co., Ltd., coronated, 3 mol of tolylene diincyanate and 1 mol of trimesololpropane, !:'!'Ji16 sintered polyisocyanate, NGO = 130%) as a solid. 12 parts per minute (30% of the functional groups of the reactive acrylic resin were initially cured) were mixed with thorough stirring. This mixture was applied to the type III surface of a PET film subjected to silicone mold release treatment using an agelator, and dried with a trowel at 80°C for 5 minutes to prepare a thermosetting sheet. The thickness of the sheet was 200 parts m.

Next, this sheet was vacuum-pressed into a dish-shaped steel plate (SS41) with a radius of 15 (2 height, 8 (to) and a bottom radius of 10 cR).
The sheet was heated to 110° C. and attached using an M-shaped mold. Add it to 160℃ for 30 minutes, IF! ! l'l&, a coating was prepared. The hardness of this coating is H on the pencil hardness scale.
1. The secretability was 100/100 in the five-way base test.

Example 15 A reactive acrylic resin (a copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, and 4-aminobutyl methacrylate, Mw = 3) was added to 300 parts of ethyl acetate.
68,000% TglO℃, OH value 40 and NH9 value 40
) 100 parts of solid content, 50 s of reactive acrylic oligomer (same as 6) solid content, 74 parts of block incyanate (same as 3) (this crosslinking agent is a mixture of Joki anti-J acrylic resin and block reactive acrylic resin). For the functional group t, LO
(having 4 isocyanate groups) and incyanate (Coronate L, manufactured by Nippon Polyurethane Industries) with a solid content of 5
．． 4 parts (10% of the total functional groups of the above-mentioned reactive acrylic resin, block reactive acrylic resin, and reactive acrylic oligomer are initially cured) were mixed with thorough stirring.

This mixture was applied with an applicator to the release surface of a PET film subjected to silicone release treatment, and dried at 70° C. for 10 minutes to produce a thermosetting sheet. The thickness of the sheet is 1
It was 100 pp1.

Next, this sheet was vacuum-adhesively molded (vacuum packaging molding) into a polyglobylene hemisphere with a radius of 12C11.
It was heated to 0° C. and attached when the ultimate vacuum level reached 10 Torr. A coating was then cured by heating at 120°C for 2 minutes and at 70°C for 1 hour. The hardness of this coating is B on the pencil hardness scale, and the adhesion is 100/10 on the 11111 width board test.
It was 0.

Example 16 300 parts of ethyl acetate IC1 reactive acrylic resin 11i (copolymer of methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid and 4-aminoethyl methacrylate, Mw==480.000. Tg 35℃
, 08 value 20 and C00H value 20 and NH, value 40) Solid content io.

30 parts of solid content of reactive acrylic oligomer (same as 6) and 53 parts of glock isocyanate (same as 1) (
This crosslinking agent is the above-mentioned reactive acrylic resin and reactive acrylic oligo! Q, has 8 equivalents of incyanate group with respect to the functional group of
J-820-60) 75 parts of the solid content (60% of the functional groups of the reactive acrylic resin are initially cured) were mixed with thorough stirring. 2. Apply this mixture to the release surface of a PET film that has been subjected to silicone release treatment using an applicator.
A thermosetting sheet was prepared by drying at 80° C. for 5 minutes. The thickness of the sheet was 60 μm.

Height: 3 eIn Next, this sheet is molded into a cylindrical shape with a radius of 10 am"? 7) In the injection mold, the sheet is fixed in a mold so that it is flat against the mold, and the polyetherimide resin is injected into the sheet. Attached.

This was cured by heating at 160° C. for 20 minutes to form a coating.

The hardness of this coating is pencil hardness, and the HB1 tightness is 1m+f.
The i-width board test was 100/1f)0.

(Effects of the Invention) The structure of the thermosetting coating sheet of the present invention is as described in the Imperial Chronicles, and it has excellent spreadability and flexibility in a state below the curing level, and can be used not only on flat surfaces but also on slightly uneven and curved surfaces. The surface of the article can be coated well without causing "wrinkles". Moreover, the thermosetting coating sheet can form a strong and uniform coating with excellent hardness and abrasion resistance by heating.

Therefore, the thermosetting coating sheet of the present invention can be used in a wide range of applications, such as for decorating the surfaces of furniture, plastic molded bodies, copper plates, etc., and as display sheet materials.

[Brief explanation of drawings]

Fig. 1 is a schematic sectional view of an embodiment of the present invention, Fig. 2 is a schematic sectional view of another embodiment of the same, Fig. 3 is a schematic sectional view of still another embodiment of the same, and Fig. 4 is a sheet. FIG. 2 is an explanatory diagram showing a falling ball test. 1. Thermosetting coating sheet, 2. Adhesive layer, 3.
- Support layer, 4... Container, 5... Steel ball. that's all

Claims (1)

[Scope of Claims] 1. An uncured thermosetting coating sheet formed of a thermosetting resin composition, wherein the thermosetting resin composition has a weight average molecular weight of 100,000 to 100,000. 1,000,000 and a reactive acrylic resin that is solid at room temperature, a blocked isocyanate, a thermoplastic resin that is solid at room temperature, and/or a reactive acrylic oligomer that has a weight average molecular weight of 1,000 to 10,000. A thermosetting coating sheet characterized by containing as a main component. 2. At least one crosslinking agent selected from the group consisting of unblocked isocyanate, melamine crosslinking agent, and epoxy crosslinking agent, the reactive acrylic resin according to claim 1, blocked isocyanate, and a solid at room temperature. Thermoplastic resin and/or weight average molecular weight of 1,000~
A semi-cured thermosetting coating sheet comprising a thermosetting resin composition containing as a main component a reactive acrylic oligomer having a molecular weight of 10,000.