TW201634306A - Decorative article and laminated body for decoration - Google Patents

Abstract

One of the embodiments of the present invention has a main object to provide a decorative article, which is capable of preventing a design of the decorative article from being impaired under high temperature environment over time, and a laminated body for decoration used for the decorative article. In one of the embodiments of the present invention, the object is attained by providing a decorative article comprising an adherend containing a resin, an adhering layer disposed on the adherend, and a decorative layer disposed on the adhering layer, wherein the adhering layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and the adhering layer includes a substance having an ester group such that the carboxyl group and the epoxy group are reacted.

Description

Decorative articles and decorative laminates

The present disclosure relates to decorative articles and decorative laminates therefor.

In a method of decorating a molded body of a resin, a method of decorating a molded body of a resin is a method of bonding a decorative laminate having a decorative layer and an adhesive layer to a surface of a molded body of a resin, in various fields such as an automobile interior member and an electric product. (Patent Documents 1 to 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-23144

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-213894

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2012-77177

It is known that when the resin is placed in a high temperature environment, there is a possibility that an escape gas is generated. Therefore, the above decorative article having a resin-containing adherend and a decorative laminate, When placed in a high-temperature environment, the adhesive layer may be peeled off due to the generation of the escaped gas, and a part of the laminate for the decorative layer may be seen from the adherend. The possibility of a problem. Further, there is a possibility that the escape gas accumulates at the above-mentioned peeling portion, causing a problem of bulging of the decorative laminate.

The present invention has been made in view of the above circumstances, and a main object of the present invention is to provide a decorative article capable of suppressing deterioration of the appearance over time in a high-temperature environment and a decorative laminate used therefor.

That is, an embodiment of the present invention includes: a resin-containing adherend, an adhesive layer disposed on the adherend, and a decorative article disposed on the adhesive layer; wherein the adhesive layer is The acrylic resin having a carboxyl group is obtained by mixing with a crosslinking agent having an epoxy group, and contains an ester group having a reaction between the carboxyl group and the epoxy group.

Furthermore, an embodiment of the present invention is a decorative article arranged in the order of a resin-containing adherend, an adhesive layer, and a decorative layer; wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the formula (1) Resin.

An embodiment of the present invention is a method for manufacturing a decorative article, comprising: preparing a step of adhering the resin to the adherend; a step of preparing the decorative laminate having the decorative layer and the adhesive layer; and a step of bonding the adherend to the adhesive layer of the laminate for the decorative layer; Next, the layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and further containing an ester group having a reaction between the carboxyl group and the epoxy group.

Furthermore, an embodiment of the present invention is a method for producing a decorative article, comprising: a step of preparing a resin-containing adherend; a step of preparing a decorative laminate having a decorative layer and an adhesive layer; and making the adherend And a step of bonding to the above-mentioned adhesive layer of the laminate for a decorative layer, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the above formula (1).

An embodiment of the present invention includes a decorative layer and a decorative layer disposed on the decorative layer, and a decorative layer for laminating the surface of the resin-containing adherend in accordance with the order of the adhesive layer and the decorative layer. The above-mentioned adhesive layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and containing an ester group having a reaction between the carboxyl group and the epoxy group.

Furthermore, an embodiment of the present invention is a decorative laminate comprising a decorative layer and a laminate layer, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the above formula (1).

The decorative article according to an embodiment of the present invention can suppress the occurrence of a high temperature environment. The style of the time is reduced.

1‧‧‧Decorative items

2‧‧‧Adhesive

3‧‧‧Next layer

4‧‧‧Decorative layer

10‧‧‧ Decorative laminate

Fig. 1 is a schematic cross-sectional view showing an example of a decorative article of the present invention.

Fig. 2 is an explanatory view showing the form of a carboxyl group-containing acrylic resin in the adhesive layer and a crosslinking agent having an epoxy group.

Fig. 3 is a schematic cross-sectional view showing an example of a laminate for decoration according to the present invention.

Hereinafter, the details of the decorative article, the method for producing the same, and the laminated body for decoration of the present embodiment will be described.

In addition, in this specification, "high temperature environment" means the environment of 80 degreeC or more.

A. Decorative items

The decorative article according to the present embodiment includes: a resin-containing adherend, an adhesive layer disposed on the adherend, and a decorative layer disposed on the adhesive layer; wherein the adhesive layer is a carboxyl group-containing acrylic The resin is obtained by mixing with a crosslinking agent having an epoxy group, and contains an ester group having a reaction of the above carboxyl group with the above epoxy group.

The decorative article of the present embodiment will be described using a drawing.

Fig. 1 is a schematic cross-sectional view showing an example of a decorative article of the embodiment. As shown in FIG. 1, the decorative article 1 of the present embodiment includes a resin-containing adherend 2, an adhesive layer 3 disposed on the adherend 2, and a decorative layer 4 disposed on the adhesive layer 3. Further, the layer 3 is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and containing an ester group having a reaction between a carboxyl group and an epoxy group.

According to the present embodiment, when the adhesive layer is obtained by mixing the acrylic resin having a carboxyl group, the adhesion of the adhesive layer to the adherend can be improved, and the adhesion between the adherend and the adhesive layer can be improved. . Therefore, when the decorative article of the present embodiment is placed in a high-temperature environment, the pressure at which the escape gas is generated from the adherend can be suppressed, and peeling occurs at the interface between the adherend and the adhesive layer.

Further, according to the present embodiment, the hardness of the adhesive layer can be improved by the fact that the adhesive layer is obtained by mixing the crosslinking agent with an epoxy group. Therefore, when the decorative article of the present embodiment is placed in a high-temperature environment, deformation or breakage of the adhesive layer due to the pressure of the evolved gas generated from the adherend can be suppressed.

Therefore, it can be a decorative article which can suppress the deterioration of the pattern over time in a high temperature environment.

As described above, the conventional decorative article may have an escape gas generated by the adherend in a high-temperature environment, thereby causing a possibility that the decorative article may have a problem of deterioration over time.

The present inventors have intensively studied this problem. First, the above problem arises because the adhesive layer is peeled off from the adherend, and thus the adhesion between the adherend and the adhesive layer is improved.

Here, in general, the adhesion between the adherend and the adhesive layer tends to be higher as the flexibility of the adhesive layer is higher. However, the present inventors newly discovered that when the adhesion between the adherend and the adhesive layer is improved by increasing the flexibility of the adhesive layer, the adhesive layer is caused by the pressure of the escape gas generated from the adherend. Deformation or damage to the body, causing the adherend The layer then peeled off. In other words, the present inventors have found that the peeling phenomenon of the decorative laminate from the adherend in a high-temperature environment is affected not only by the adhesion between the adherend and the adhesive layer but also by the self-hardness of the adhesive layer. This embodiment is characterized by having such discovered features.

According to the present embodiment, by including an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, both the adhesion between the adherend and the adhesive layer and the hardness of the adhesive layer can be achieved. .

Hereinafter, each configuration of the decorative article of the present embodiment will be described.

Subsequent layer

The adhesive layer of this embodiment is disposed on the adherend. Further, the subsequent layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and further comprising an ester group having a reaction between the carboxyl group and the epoxy group.

Further, the raw material of the adhesive layer contains an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group. Further, the subsequent layer has an ester group which is mixed with the materials and reacts with a carboxyl group and an epoxy group.

In the adhesive layer, as shown in FIG. 2, the carboxyl group-containing acrylic resin X and the epoxy group-containing crosslinking agent Y are mixed and used, and have the following formula in which the carboxyl group and the epoxy group are reacted. (1) The ester group shown. Further, by having the above ester group, the acrylic resin X and the crosslinking agent Y have a crosslinked structure Z. The crosslinked structure Z is a three-dimensional network structure.

In addition, Figure 2 shows the acrylic resin with carboxyl group in the relevant adhesive layer. Description of the form after crosslinking with an epoxy group-containing crosslinking agent pair.

In other words, in the present embodiment, a decorative article may be provided in the order of a resin-containing adherend, an adhesive layer, and a decorative layer, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the above formula (1).

Hereinafter, the carboxyl group-containing acrylic resin and the epoxy group-containing crosslinking agent and the like of the adhesive layer material used in the present embodiment will be described.

(1) Acrylic resin with carboxyl group

The acrylic resin having a carboxyl group is used as a main component of the adhesive layer to form an adhesive layer. The acrylic resin is a polymer comprising acrylic acid, methacrylic acid, and the like.

The carboxyl group-containing acrylic resin is not particularly limited as long as it can form a crosslinked structure with a crosslinking agent having an epoxy group and can impart a desired adhesiveness, and the rest thereof is not particularly limited, and for example, (meth) acrylate, A copolymer which is copolymerized with a monomer having a carboxyl group.

The term "(meth)acrylic acid" means acrylic acid or methacrylic acid. Further, the term "(meth)acrylate" as used hereinafter means acrylate or methacrylate.

As the (meth) acrylate type, for example, methyl (meth) acrylate or (methyl) can be used. Ethyl acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate Ester, stearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and the like. These acrylates may contain one type or two or more types.

The (meth) acrylate is used as a main component of a carboxyl group-containing acrylic resin. Here, the "main component" is more than the other components with respect to the acrylic resin having a carboxyl group, and the content of the (meth) acrylate is preferably 51% by mass or more by mass.

Further, in the present embodiment, the total amount of the (meth) acrylate is preferably in the range of 51% by mass to 98% by mass, more preferably 90% by mass based on the acrylic resin having a carboxyl group. Within 98% by mass.

The reason is that when the content of the (meth) acrylate is too large, the relative content of the monomer having a carboxyl group is less, and thus it is difficult to impart a desired adhesion to the adhesive layer.

As a single system having a carboxyl group, for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, (A) Monoethyl acrylate succinic acid, monohydroxyethyl (meth) acrylate, monohydroxyethyl (meth) acrylate, monohydroxyl (meth) acrylate Ester, 1,2-dicarboxycyclohexane monohydroxyethyl (meth)acrylate, (meth)acrylic acid dimer, ω-carboxy-polycaprolactone mono(meth)acrylate, and the like. Single system with carboxyl groups It may contain one type or two or more types.

The content of the monomer having a carboxyl group is not particularly limited as long as the desired adhesiveness can be imparted to the adhesive layer, and is preferably 0.1 part by weight based on 100 parts by weight of the (meth) acrylate. Within the range of 15 parts by weight, more preferably in the range of 0.1 parts by weight to 10 parts by weight. The reason is that if the content of the monomer having a carboxyl group is too small, there is a possibility that it is difficult to impart a desired adhesion to the adhesive layer, and if the monomer content of the carboxyl group is excessive, the acrylic resin having a carboxyl group is used. Subsequent sexuality is too high, making it more difficult to form the self-body of the subsequent layer, or the possibility of being difficult to access.

The carboxyl group-containing acrylic resin may be optionally added with other components in addition to the (meth) acrylate and the carboxyl group-containing monomer. The above-mentioned other components are, for example, a hydroxyl group-containing (meth) acrylate monomer, a propylene group-containing (meth) acrylate monomer, and a guanamine-containing group as described in JP-A-2014-148570. Methyl) acrylate monomer and the like.

The method for synthesizing the carboxyl group-containing acrylic resin is obtained by polymerizing the above (meth) acrylate, a monomer having a carboxyl group, and other monomers as necessary, by a usual polymerization method. The polymerization method may be, for example, a solution polymerization, a bulk polymerization, an emulsion polymerization or a suspension polymerization, and particularly preferably a solution polymerization. The solvent used in the solution polymerization may be, for example, an organic solvent such as ethyl acetate, toluene, n-hexane, acetone or methyl ethyl ketone. Further, as a polymerization initiator used in the polymerization, for example, a peroxide such as benzamidine peroxide or lauryl peroxide; an azobis compound such as azobisisobutyronitrile or azobisvaleronitrile or Polymer azo polymerization initiator, etc., these systems can be individually Use, or in combination. Further, in the above polymerization, in order to adjust the molecular weight of the carboxyl group-containing acrylic resin, a conventionally known chain transfer agent can be used.

The weight average molecular weight of the acrylic resin having a carboxyl group is not particularly limited as long as it imparts desired adhesiveness and hardness to the adhesive layer, and is preferably in the range of 200,000 to 2,000,000, particularly preferably in the range of 200,000 to 2,000,000. Within the range of 500,000~1,500,000, the best range is in the range of 500,000~1,000,000.

The reason is that if the weight average molecular weight of the acrylic resin having a carboxyl group is too small, there is a possibility that it is difficult to form a desired hardness of the adhesive layer. Moreover, the reason is that if the weight average molecular weight of the acrylic resin having a carboxyl group is too large, the adhesion between the adherend and the adhesive layer may be sufficiently difficult.

The weight average molecular weight of the carboxyl group-containing acrylic resin was determined by a gel permeation chromatography (GPC) to obtain a weight average molecular weight (Mw) value in terms of standard polystyrene. For the specific measurement conditions, Waters 2695 manufactured by Waters was used as the measurement device, and LF-804×3 (inner diameter: 8 mm, length: 300 mm) manufactured by Showa Denko Corporation was used as the column system, and the sample concentration was set to 0.5% (diluted with tetrahydrofuran). The phase solvent system used tetrahydrofuran, the flow rate was set to 1 ml/min, and the column temperature was set to 40 °C.

The acid value of the acrylic resin having a carboxyl group is removed before the adhesion between the adherend and the adhesive layer can be formed, and the rest is not particularly limited, and is preferably 0.01 mgKOH/g to 20 mgKOH/g. Within the range, it is particularly preferably in the range of 0.01 mgKOH/g to 15 mgKOH/g.

The reason is that if the acid value is too small, it is difficult to impart a desired adhesive force to the adhesive layer, and there is a possibility that it is difficult to make the adhesion between the adherend and the adhesive layer favorable. Again, if on When the acid value is too large, for example, the adhesion of the acrylic resin having a carboxyl group is too high, which may make it difficult to form a self-adhesive layer or may be difficult to access.

The above acid value means the number of milligrams of potassium hydroxide required when neutralizing the acidic component contained in 1 g of the sample. Further, the acid value can be measured in accordance with JIS K 0070-1992.

The glass transition temperature (Tg) of the carboxyl group-containing acrylic resin is improved in the high-temperature environment before the adhesion between the adherend and the adhesive layer is good, and the rest is not particularly limited, and is preferably -30. In the range of °C~25°C, especially better in the range of -30°C~15°C, and especially in the range of -10°C~10°C.

The reason is that if the Tg of the carboxyl group-containing acrylic resin is too low, it is difficult to make the hardness of the adhesive layer good in a high temperature environment, and if the Tg of the carboxyl group-containing acrylic resin is too high, There is a possibility that it is difficult to make the adhesion of the adherend to the adhesive layer sufficient.

The above Tg system uses a solid viscoelasticity analyzer RSA-III manufactured by DSC and TA Instruments, according to the dynamic viscoelasticity measurement method according to JIS K7244-1 [attachment mode: compression mode, frequency: 1 Hz, temperature: - The measured value was measured at 50 ° C to 150 ° C and a temperature increase rate of 5 ° C / min. Further, the peak value of tan δ is referred to as "Tg".

(2) an epoxy group-containing crosslinking agent

The epoxy group-containing crosslinking agent crosslinks the above carboxyl group-containing acrylic resin.

The crosslinking agent having an epoxy group may, for example, be a polyfunctional epoxy compound having a plurality of epoxy groups in one molecule. The number of epoxy functional groups in the relevant molecule is not particularly limited, and among them, a tetrafunctional epoxy system having four epoxy groups in one molecule is preferably used. Compound. The reason is that the hardness of the adhesive layer can be easily adjusted while maintaining the adhesion between the adherend and the adhesive layer.

The crosslinking agent having an epoxy group may specifically be, for example, sorbitol polyepoxypropyl ether, polyglycerol polyepoxypropyl ether, pentaerythritol glycopropyl ether, trimethylolpropane polyepoxypropyl group. Ether, glycerol polyepoxypropyl ether, neopentyl glycol epoxy propyl ether, resorcinol diepoxypropyl ether, m-xylene bisamine tetraepoxypropyl ether, and the like, and the like . In particular, this embodiment is preferably m-xylene bisamine tetraepoxypropyl ether and a hydride thereof. The reason is that the hardness of the adhesive layer can be easily adjusted while maintaining the adhesion between the adherend and the adhesive layer.

The content of the crosslinking agent having an epoxy group is not particularly limited, and is preferably in the range of 0.01 part by weight to 2.0 parts by weight, more preferably in the range of 100 parts by weight based on the carboxyl group-containing acrylic resin. 0.01 parts by weight to 1.0 parts by weight, particularly preferably 0.01 parts by weight to 0.1 parts by weight. The reason is that if the content of the epoxy group-containing crosslinking agent is too small, it is difficult to impart sufficient hardness to the adhesive layer, and if the content of the epoxy group-containing crosslinking agent is excessive, then If the layer is too hard, there is a possibility that it is difficult to make the adhesion between the adherend and the adhesive layer sufficient.

(3) Additives

The adhesive layer of the present embodiment is not particularly limited as long as it contains the above-mentioned carboxyl group-containing acrylic resin and the epoxy group-containing crosslinking agent, and may be appropriately selected as necessary.

(a) Low molecular additives

In the adhesive layer, it is preferable to contain an additive having a weight average molecular weight smaller than that of the above-mentioned carboxyl group-containing acrylic resin (hereinafter, referred to as "low molecular additive"). The reason is that by including a low-molecular additive in the adhesive layer, it is possible to improve the effect of suppressing the deterioration of the pattern over time in a high-temperature environment. Although the reason for this is not necessarily clear, it can be presumed as follows.

Here, even if the surface of the adherend is considered to have smoothness, fine irregularities having a micron-order depth are usually present. Therefore, when an adhesive layer is disposed on the adherend, a slight gap may occur between the adherend and the adhesive layer. In particular, when the adhesive layer is hard, the adhesive layer is difficult to trace the adherend, and thus it is presumed that the above-mentioned gap is likely to occur. Moreover, when the decorative article has the above gap between the adherend and the adhesive layer, the evolved gas generated in the high temperature environment easily flows into the gap, and it is presumed that the pressure of the escape gas of the gap is increased, resulting in being stuck. Peeling is likely to occur between the object and the adhesive layer.

On the other hand, when the low-molecular weight additive is contained in the adhesive layer, it is estimated that the adhesive layer can easily trace the fine unevenness of the adherend, and the occurrence of the gap can be suppressed.

As the low molecular weight additive, for example, a tackifier or a heat resistance imparting agent can be used. The following description will be respectively made.

(i) adhesion agent

In the present embodiment, the adhesive layer preferably further contains an adhesive. The tackifier is an amorphous oligomer having a weight average molecular weight of 400 to 3,000. By mixing with a carboxyl group-containing acrylic resin, it can impart fluidity and viscosity, and has an improved adhesion. The function. Further, the method for measuring the weight average molecular weight is the same as the method for measuring the weight average molecular weight of the above-mentioned carboxyl group-containing acrylic resin.

The tackifier can be roughly classified into two types, that is, a natural resin system and a synthetic resin system. This embodiment is preferably a natural resin type, and more preferably contains at least one of a rosin type and a terpene type.

Examples of the rosin system include rosin, and rosin derivatives such as hydrogenated rosin, disproportionated rosin, polymerized rosin, and esterified rosin. The rosin system may be used singly or in combination of two or more.

Examples of the terpene-based system include a terpene-based resin, a terpene-based resin, an aromatic modified terpene-based resin, and a hydrogenated terpene-based resin. The above terpenes may be used singly or in combination of two or more.

Further, a styrene-based elastomer can also be used as the binder. Specifically, a known styrene-based elastomer having a hard segment in a polystyrene phase can be used. Specifically, for example, styrene-butadiene copolymer (SBR), styrene-isoprene-styrene copolymer (SIS), styrene-butadiene-styrene copolymer (SBS), styrene - a copolymer of styrene and a diene such as a vinyl isoprene-styrene polymer, and such a hydride (for example, ethylene-ethylene-butadiene-styrene copolymer (SEBS), etc.), styrene- Isobutylene-styrene triblock copolymer (SIBS), styrene-isobutylene diblock copolymer (SIB). These styrene-based elastic systems may be used singly or in combination of two or more.

The content of the adhesive is removed before the desired adhesive force can be imparted to the adhesive layer, and the rest is not particularly limited, and the weight is 100% relative to the acrylic resin having a carboxyl group. The portion is preferably 20 parts by weight or less, particularly preferably 5 parts by weight to 15 parts by weight.

The reason is that if the content of the binder is excessive, the compatibility between the binder and the acrylic resin having a carboxyl group may be lowered to cause bleeding.

(ii) heat resistance imparting agent

In the present embodiment, the adhesive layer preferably further contains a heat-resistant imparting agent.

The heat-resistant imparting agent is a resin having a weight average molecular weight of 50,000 to 200,000, and by blending with a carboxyl group-containing acrylic resin, the hardness of the adhesive layer in a high temperature environment can be further enhanced. Further, the method for measuring the weight average molecular weight is the same as the method for measuring the weight average molecular weight of the carboxyl group-containing acrylic resin.

The heat-resistant imparting agent is not particularly limited as long as the weight average molecular weight is within the above range, and may be, for example, an acrylic resin or an acrylic polymer having an acrylic monomer as an essential monomer component. The monomer component constituting the acrylic resin (acrylic polymer) may be, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate or isopropyl (meth)acrylate. Ester, butyl (meth)acrylate, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, (methyl) Octyl acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc. a (meth)acrylic acid alkyl ester of a branched chain alkyl group; a carboxyl group-containing polymerizable unsaturated compound such as (meth)acrylic acid, crotonic acid, itaconic acid, fumaric acid or maleic acid or Anhydride; 2-hydroxymethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) propylene A hydroxyl group-containing (meth) acrylate such as acid-6-hydroxyhexyl ester, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate or the like.

Further, in addition to the above, for example, a cycloalkyl (meth)acrylate such as cyclohexyl (meth)acrylate; N-hydroxymethyl(meth)acrylamide, N-butoxy (meth)acrylic acid decylamine derivatives such as methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide ; (meth)ethyl methacrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, (A) a dialkylaminoalkyl (meth)acrylate such as dipropylaminopropyl acrylate; a styrenic compound such as styrene, vinyl toluene or α-methylstyrene; vinyl acetate, vinyl propionate Vinyl esters such as esters; vinyl halides such as vinyl chloride; vinyl ethers such as methyl vinyl ether; vinyl compounds containing cyano groups such as (meth)acrylonitrile; and olefins such as ethylene and propylene, and diene. The unsaturated compound is used as a monomer component.

In the present embodiment, from the viewpoint of compatibility, the heat-resistant imparting agent is preferably an acrylic resin having a structure similar to that of the acrylic resin of the main component carboxyl group. Specifically, it is preferably an acrylic resin containing a skeleton similar to the acrylic resin of the main component carboxyl group.

The content of the heat-resistant imparting agent is not particularly limited as long as the desired hardness can be imparted to the adhesive layer, and is preferably 20 parts by weight or less based on 100 parts by weight of the acrylic resin having a carboxyl group. More preferably, it is in the range of 5 parts by weight to 15 parts by weight. The reason is that if the content of the heat-resistant imparting agent is excessively large, the compatibility between the heat-resistant imparting agent and the acrylic resin having a carboxyl group may be lowered to cause bleeding.

(b) Isocyanate compounds

In the present embodiment, the adhesive layer may further contain an isocyanate compound. The reason is that if the adhesive layer contains an isocyanate-based compound, the adhesion between the adherend and the adhesive layer can be improved by the interaction between the molecules on the surface of the adherend and the isocyanate compound contained in the adhesive layer.

As the isocyanate-based compound, for example, a compound which is an isocyanate-based crosslinking agent can be contained in a general adhesive. Specifically, for example, an isocyanate compound described in JP-A-2012-213894 can be used.

The content of the isocyanate-based compound is not particularly limited. For example, it is preferably in the range of 0.1 part by weight to 3 parts by weight based on 100 parts by weight of the acrylic resin having a carboxyl group. The reason is that if the content of the isocyanate-based compound is excessively large, the subsequent layer becomes too hard, and there is a possibility that the adhesion between the adherend and the adhesive layer is lowered.

(c) other additives

The adhesive layer of this embodiment may further contain other additives such as an ultraviolet absorber, an antioxidant, a filler, a pigment, an antistatic agent, a fluorescent whitening agent, and the like.

(4) Next layer

The layer is then disposed between the adherend and the decorative layer. Further, the adhesive layer is usually formed in advance on the decorative layer to form a decorative molded body having a decorative layer and an adhesive layer. Adhesive fit.

The thickness of the layer is not limited to the extent that it can be disposed on the decorative layer and can be attached to the surface of the adherend together with the decorative layer, and can be appropriately adapted to the use of the decorative article of the embodiment. select. The thickness of the layer is preferably in the range of, for example, 10 μm to 100 μm, more preferably in the range of 30 μm to 50 μm. The reason is that if the thickness of the adhesive layer is thin, there is a possibility that it is difficult to adhere the adhesive layer well to the adherend, or it is difficult to form an adhesive layer on the decorative layer. In addition, when the thickness of the adhesive layer is thick, when the decorative layer is formed on the decorative layer and then laminated on the adherend, the decorative laminate is likely to wrinkle. Also, the reasons are related to cost increases.

Here, the "thickness" of each member means the thickness obtained by a general measurement method. As a method of measuring the thickness, for example, a stylus type method in which a surface is detected by a stylus, and a thickness is calculated, an optical method in which a thickness is calculated from a spectral reflectance spectrum, and the like can be used. Further, the thickness may be an average value of thickness measurement results at a plurality of places of the object member.

The 25 ° C storage elastic modulus of the layer is then removed before the decorative article can be formed, and the rest is not particularly limited, and is preferably in the range of 1.0×10 ⁴ Pa to 1.0×10 ⁹ Pa, and more preferably 1.0. ×10 ⁴ Pa~1.0×10 ⁶ Pa.

The reason is that if the storage modulus of the adhesive layer at 25 ° C is too low, it is difficult to form the self-body of the adhesive layer, and if the storage modulus of the adhesive layer at 25 ° C is too high, it will be difficult. The possibility of making the adhesion of the adherend to the adhesive layer sufficient.

Further, the storage elastic modulus in the range of 100 ° C to 140 ° C as the adhesive layer is not particularly limited as long as the adhesive layer can be disposed on the surface of the adherend, and is preferably 1.0 × 10 ⁵ Pa. ~1.0×10 ⁶ Pa range. The reason is that if the storage elastic modulus of the adhesive layer is too low, the adhesive layer in a high temperature environment cannot be formed to have a desired hardness, and the adhesive layer may be deformed or damaged due to the escape gas generated by the adherend. The possibility. Further, the reason is that if the storage elastic modulus of the adhesive layer is too high, there is a possibility that it is difficult to make the adhesion between the adherend and the adhesive layer sufficient.

The storage elastic modulus indicates the ease of deformation of the resin, and can be measured in accordance with the method according to JIS K7244-1 and JIS K7244-4. Specifically, it can be measured using a commercially available viscoelasticity measuring device. For example, using Rheometrics' solid-state viscoelastic analyzer RSA-II, for a sample with a width of 5 mm, according to the stretching mode, the holding distance is 10 mm, the measuring frequency is 1 Hz, the measuring temperature is -50 ° C to 150 ° C, and the heating rate is 5 ° C / min. The measurement was carried out under the conditions.

The adhesive strength as the adhesive layer is not particularly limited as long as the adherend can be placed in close contact with the adhesive layer. For example, the 180° peeling force of the polycarbonate at 25° C. is 1 N/25 mm to 50 N/25 mm. Within the range, it is particularly preferably in the range of 1 N/25 mm to 40 N/25 mm. The reason is that the adhesion between the adherend and the adhesive layer is good by the adhesive strength of the adhesive layer within the above range.

Further, the adhesive strength as the adhesive layer is, for example, a 180° peeling force against polycarbonate at 110 ° C, in the range of 1 N/25 mm to 20 N/25 mm, particularly preferably in the range of 1 N/25 mm to 10 N/25 mm. The reason is that the adhesion strength of the layer is above Within the range, the adhesion between the adherend and the adhesive layer is good.

The adhesive strength of the above-mentioned adhesive layer was obtained by cutting a double-sided adhesive film provided with an adhesive layer into a test piece having a width of 25 mm, and adhering it to a polyethylene terephthalate substrate in accordance with JIS Z0237. The roller having a mass of 2 kg was reciprocated twice, and the test body was adhered to a polycarbonate substrate, and the peel strength was measured at a peeling speed of 0.3 m/min and a peeling angle of 180°.

In the method of forming the adhesive layer of the present embodiment, for example, a composition for an adhesive layer containing each component of the adhesive layer and a solvent capable of dissolving (or dispersing) the respective components is prepared, and the composition for the adhesive layer is coated. It can be formed on the decorative layer or on the release layer. The relevant solvent can be used in the same manner as those used in general adhesives. Further, the relevant coating method can be applied by a known method using, for example, a gravure coating method, a roll coating method, a comma wheel coating method, or a gravure reverse roll coating method, and drying. Can be formed. Further, the adhesive layer can also be formed by a printing method. As the printing method, for example, a gravure printing method, a screen printing method, or the like can be given.

The coating film of the composition for the above-mentioned adhesive layer may be subjected to an aging treatment as needed.

2. Decorative layer

The decorative layer of this embodiment is disposed on the adhesive layer. In addition, the decorative layer and the subsequent layer may be disposed in direct contact with each other, or may be disposed in a different layer between the decorative layer and the subsequent layer.

Further, in the present embodiment, the decorative article can be manufactured by laminating the decorative laminate provided with the decorative layer and the adhesive layer on the adherend. For example, it can be produced by a vacuum forming method, and in the case of the decorative layer, a vacuum forming method can be used.

The decorative layer usually has a substrate containing a thermoplastic resin, and the substrate is decorated. Further, the base material is usually one which has ductility, shape traceability, and tortuosity.

As the substrate used for the decorative layer, for example, a thermoplastic resin can be used. Since the thermoplastic resin system can be the same as that of the user of the general decorative film, the description thereof will be omitted.

The thickness of the substrate is removed before being disposed on the adherend, and the rest is not particularly limited, and is, for example, in the range of 25 μm to 500 μm, particularly preferably in the range of 50 μm to 200 μm.

The storage elastic modulus of the substrate in the range of 100 ° C to 140 ° C is preferably in the range of 1 × 10 ⁵ Pa to 1 × 10 ⁸ Pa. When the storage elastic modulus of the substrate is within the above range, the decorative layer having good tracking property to the surface of the adherend can be obtained.

The storage elastic modulus of the substrate was measured by DSC, TA Instruments, a solid viscoelastic analyzer RSA-III, and the dynamic viscoelasticity measurement according to JIS K7244-1 (adhesion mode: three-point bending mode, frequency: 1 Hz, temperature: -50 ° C ~ 150 ° C, heating rate: 50 C / min) measured values.

The decorative layer is decorated with the above substrate. The decorative system may be formed into a concave-convex shape by the substrate itself or may be colored. Further, a decorative layer may be additionally provided in addition to the substrate. The decorative layer can be, for example, a pigment-containing coloring layer, a metal film layer, or the like. The decorative layer can be, for example, described in Japanese Laid-Open Patent Publication No. 2012-213894.

3. Viscous

The adherend of the present embodiment contains a resin. Resin-containing adherends are likely to generate evolved gases when placed in a high temperature environment.

The term "escape gas" as used herein refers to a gas generated by volatilization of moisture in a resin contained in an adherend, and residues of a resin material, an organic substance such as a decomposition product, and the like.

The adherend system may contain a resin as long as it contains a resin, and may contain a resin on at least a part of the surface of the adherend. The reason is that even if the evolved gas generated inside the adherend, it will spread to the outside. Originally, when the surface of the adherend contains a resin, since the surface of the adherend becomes a portion in direct contact with the adhesive layer, the escape gas has a greater influence on the adhesive layer. Therefore, it is more preferable that the surface of at least a part of the adherend contains a resin. The reason is that when the surface of the adherend contains a resin, the adhesive layer provided in the present embodiment can achieve a higher effect. The surface of the adherend may also contain a resin as a whole.

The resin to be used as the adherend is removed before the escape gas can be generated in a high-temperature environment, and the rest is not particularly limited, and a resin contained in a general resin molded body can be used. The resin to be used as the adherend may specifically be, for example, an acrylic resin, a polyester resin, a polystyrene resin, or a polyolefin resin such as polypropylene; an acrylonitrile-butadiene-styrene copolymer (ABS resin) ), a polycarbonate resin, a phenol resin, a vinyl chloride resin, a cellulose resin, and a rubber.

Further, among the above resins, acrylic resins, polystyrene resins, and acrylic resins are preferred. Acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin. The reason is that if the above-mentioned resin is contained in the adherend, it is easy to generate an escape gas from the adherend in a high-temperature environment, and therefore, by adopting the configuration of the decorative article of the present embodiment, it is possible to improve the occurrence of a decrease in the pattern in a high-temperature environment. Effect.

From the viewpoint of heat resistance and mechanical strength of the adherend, ABS resin or polycarbonate resin can be preferably used.

The form of the adherend can be appropriately selected in accordance with the form of the decorative article of the present embodiment, and is, for example, a flat plate shape, a curved plate shape, a film shape, or a three-dimensional three-dimensional shape. In the present embodiment, the form of the adherend is preferably a three-dimensional three-dimensional shape. The reason is that the adhesive layer and the decorative layer can be placed on the adherend by a vacuum forming method such as the TOM method.

Further, as a form of the adherend, it is preferable that at least a part of the surface of the surface on which the adhesive layer and the decorative layer are disposed is provided with a concave-convex surface of the concave portion and the convex portion or a curved surface having a curved portion. The reason is that since the adhesive layer provided in the present embodiment has moderate flexibility, it has an advantage that it can be closely adhered to the uneven surface or the curved surface. Further, the reason is that when the adhesive layer and the decorative layer are adhered to the uneven surface or the curved surface of the adherend, stress is applied to the adhesive layer and the decorative layer, so that it is easily affected by the evolved gas generated from the adherend, but The adhesion layer provided in the present embodiment can suppress this influence.

Therefore, in the decorative article of the present embodiment, it is preferable that at least a part of the surface of the adherend has a concave-convex surface provided with a concave portion and a convex portion, or a curved surface having a curved portion, and the uneven surface or the curved surface passes through the adhesive layer Next to the decorative layer described above. Moreover, in this case, it is more preferable that the above-mentioned adhesive layer is attached to the uneven surface of the decorative layer or the above The curved surface contains a resin.

As a method of forming the adherend, a general method of forming a resin molded body can be used, and specifically, for example, an extrusion molding method, an injection molding method, or the like can be used.

The adherend may contain only a resin, and an inorganic material or wood may be added to the resin. Alternatively, a laminate of at least one of a resin layer, an inorganic material layer, and a wood layer is formed.

4. Method of manufacturing decorative articles

The manufacturing method of the decorative article of the present embodiment is carried out before the layers can be placed in the order of the adhesive layer and the decorative layer on the surface of the adherend, and the rest is not particularly limited.

For example, the method for producing an embodiment decorative article includes a step of preparing a decorative laminate having a decorative layer and an adhesive layer, and a step of bonding the adherend to the adhesive layer of the laminate for the decorative layer.

For the method of bonding the adherend to the decorative laminate, for example, a vacuum forming method can be used. Further, when the adherend has a three-dimensional three-dimensional shape, it is preferable to use the TOM method in the vacuum forming method.

Further, in the step of bonding the adherend to the decorative laminate, it is preferable to perform at least one of a heating operation, a press operation, and a pressure reduction operation. By performing the above operation when the adherend is bonded to the decorative laminate, the adhesion between the adherend and the decorative laminate can be improved. The reason is that since the adhesive layer of the present embodiment has heat resistance and moderate flexibility due to the crosslinked structure, even if such operation is performed The advantages of bad conditions are still not easy to occur. These operations can be performed in a known manufacturing process such as a hot press method, a hot press method, a vacuum press method, a pneumatic method, an insert molding method, an in-mold forming method, a vacuum forming method such as a TOM method, or the like.

The vacuum forming method generally includes a heating step of softening the decorative layer by heating the decorative laminate to adhere the adherend to the decorative laminate.

The heating temperature of the decorative laminate in the heating step can be appropriately selected in accordance with the type of the decorative laminate and the adherend, and is not particularly limited, but is preferably in the range of, for example, 100 ° C to 140 ° C. Moreover, the heating time of the decorative laminate for the heating step is preferably in the range of, for example, 10 seconds to 120 seconds.

A known method can be applied to both the related vacuum forming method and the TOM method.

5. Use

The decorative article of the present embodiment is applied to, for example, an automobile interior member, an electric product, a miscellaneous goods, or the like. Among them, the decorative article of the present embodiment is preferably applied to an automobile interior member.

B. Decorative laminate

In the decorative layering system of the present embodiment, the decorative layer and the adhesive layer disposed on the decorative layer are provided, and the surface of the adherend containing the resin is sequentially laminated in accordance with the adhesive layer and the decorative layer; The adhesive layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and further comprising an ester group having a reaction between the carboxyl group and the epoxy group.

The decorative laminate of the present embodiment will be described with reference to the drawings.

Fig. 3 is a schematic cross-sectional view showing an example of a laminate for decoration. As shown in FIG. 3, the decorative laminated body 10 of the present embodiment includes a decorative layer 4 and an adhesive layer 3 disposed on the decorative layer 4. Next, the layer 3 is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and containing an ester group having a reaction between a carboxyl group and an epoxy group. Further, the decorative laminate system of the present embodiment is used for the production of the decorative article 1 illustrated in Fig. 1, and the surface of the resin-containing adherend 2 is laminated in the order of the adhesive layer 3 and the decorative layer 4.

According to the present embodiment, by using the decorative laminate of the present embodiment to produce a decorative article, it is possible to obtain a decorative article capable of suppressing deterioration of the appearance over time in a high-temperature environment.

The details of the decorative layer and the subsequent layer of the decorative laminated body of the present embodiment are the same as those described in the above-mentioned "A. Decorative laminated body", and thus will not be described herein.

The decorative laminate of the present embodiment may be provided with a release layer on the adhesive layer as needed. The reason is that the laminate for the decorative layer can be easily handled.

The peeling layer can be the same as that of a user such as a general adhesive sheet, and for example, a peeling layer described in JP-A-2012-213894 can be used.

The decorative laminate system of the present embodiment is applied to the surface of the resin-containing adherend according to The adhesive layer and the decorative layer are sequentially laminated and used. In the present embodiment, the decorative laminate is preferably disposed on the surface of the adherend by a vacuum forming method. The reason is that the decorative laminate can be well bonded to the surface of the adherend.

In the present embodiment, a decorative laminate comprising a decorative layer and a laminate layer may be provided, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the above formula (1).

This embodiment is not limited to the above embodiment. The above-described embodiments are merely illustrative, and those having substantially the same configuration as the technical idea described in the claims of the present embodiment can achieve the same effects and are included in the technical scope of the present embodiment.

[Examples]

The present embodiment will be described in more detail with reference to examples and comparative examples.

[Example 1]

100 g of an acrylic adhesive having a carboxyl group (made by Synthetic Chemical Co., Ltd., SK-DYNE 1838, solid content: 21%), and an epoxy-based crosslinking agent (manufactured by Synthetic Chemical Co., Ltd., E-AX, solid content) 5%) 0.15 g, 5 g of ethyl acetate (manufactured by DIC Graphics) as a diluent for viscosity adjustment, to obtain a composition for an adhesive layer. Then, the composition for the subsequent layer was dried to a thickness of 30 μm, and applied to a PET carrier film (manufactured by Toyobo Co., Ltd.: E7304) having a thickness of 38 μm which had been subjected to polyfluorination stripping treatment by a coater. After drying at 100 ° C for 2 minutes, 200 μm ABS used as a substrate on the laminate A film (made of DNP) was used to obtain a decorative laminate having a substrate and an adhesive layer. The above-mentioned adhesive layer was subjected to an aging treatment for 3 days in an environment of 40 °C.

[Embodiment 2]

A laminate for decoration was obtained in the same manner as in Example 1 except that 10.5 g of TACKIFIRE (manufactured by Arakawa Chemical Co., Ltd., PINECRYSTAL® KE359, and 20% solid content) was added to the production of the composition for the adhesive layer.

[Example 3]

In addition to the production of the composition for the adhesive layer, styrene monomer and aliphatic monomer copolymer (manufactured by Mitsui Chemicals Co., Ltd., FTR-6100, solid fraction 25%) were added at 8.4 g, In the same manner as in Example 1, a decorative laminate was obtained in the same manner.

[Example 4]

In the same manner as in Example 1, except that 21 g of a low molecular weight acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., DIANAL® MR-83, solid content: 10%) was added in the production of the composition for the adhesive layer. Decorative laminate.

[Examples 5 to 26]

In the same manner as in Example 1, except that the main component, the crosslinking agent, and the additive were blended in the ratios shown in the following Tables 1 to 3, the decorative laminates were obtained in the same manner as in Example 1.

In Tables 1 to 3, SK-DYNE 2094 is an acrylic adhesive having a carboxyl group (manufactured by Soken Chemical Co., Ltd., SK-DYNE 2094, 25% solid content); E-5CM is a ring. Oxygen-based cross-linking agent (manufactured by Soken Chemical Co., Ltd., E-5CM, solid content 5%); DIANAL® BR-80 is a low molecular weight acrylic resin (Mitsubishi®, DIANAL® BR-80) ), a solution dispersed in methyl ethyl ketone in a form of 10% solid content; DIANAL® BR-84 means low molecular weight acrylic resin (made by Mitsubishi Rayon Co., Ltd., DIANAL® BR-84) a solution in which 10% is dispersed in methyl ethyl ketone; FTR-0105 is a method in which a styrene monomer and an aliphatic monomer are copolymerized (Mitsui Chemical Co., Ltd., FTR-0105), and the solid content is 25%. a solution dispersed in methyl ethyl ketone; FTR-8120 is a copolymer of styrene monomer and aliphatic monomer (manufactured by Mitsui Chemicals Co., Ltd., FTR-8120), dispersed in methyl ethyl ketone according to a solid content of 25%. The solution. Further, in the respective components, those having a carboxyl group are referred to as "CO-containing", and those having no carboxyl group are referred to as "Non-COOH".

[Comparative Example 1]

100 g of an acrylic adhesive (made of Synthetic Chemical Co., Ltd., SK-DYNE 1811L, 23% solid content) having no carboxyl group, and an epoxy-based crosslinking agent (made by Synthetic Chemical Co., Ltd., E-AX, solid type) 5%) 0.055 g of ethyl acetate (manufactured by DIC Graphics) of a diluent for viscosity adjustment was adjusted to 5 g to obtain a composition for an adhesive layer. In the same manner as in Example 1, the subsequent steps were carried out to obtain a decorative laminate.

[Comparative Example 2]

100 g of an acrylic adhesive (manufactured by Konica Minolta Co., Ltd., SK-DYNE 1811L, 23% solids) having no carboxyl group, and an isocyanate-based crosslinking agent (Total Chemical Co., Ltd., TD-75, 2 g of a solid content of 2 g and 5 g of ethyl acetate (manufactured by DIC Graphics) of a diluent for viscosity adjustment were used to obtain a composition for an adhesive layer. Subsequent steps In the same manner as in Example 1, a decorative laminate was obtained.

The composition formula for the adhesive layer of the relevant comparative example is shown in Table 3.

[Evaluation]

The decorative laminates of the above-described Examples 1 to 26 and Comparative Examples 1 and 2 were bonded to ABS/PC molding resin (10 cm × 12 cm × 1 cm by DNP) by a TOM method to obtain an evaluation sample. The bonding temperature in the TOM method was set to 120 °C.

The evaluation sample was placed in an oven at 110 ° C for 250 hours, and the change in appearance was visually confirmed. The results are shown in Tables 1-3.

Evaluation basis

○: No foaming was observed in the surface.

×: Foaming was found in the surface.

As shown in Tables 1 and 2, the evaluation samples of Examples 1 to 26 showed no foaming in the surface, and it was possible to suppress the deterioration of the pattern over time in a high-temperature environment. On the other hand, as shown in Table 3, the evaluation samples of Comparative Examples 1 and 2 were found to have foamed in the surface, and it was confirmed that the temporal deterioration of the sample was observed in a high temperature environment.

1‧‧‧Decorative items

2‧‧‧Adhesive

3‧‧‧Next layer

4‧‧‧Decorative layer

Claims (14)

A decorative article comprising: a resin-containing adherend, an adhesive layer disposed on the adherend, and a decorative layer disposed on the adhesive layer, wherein the adhesive layer is a carboxyl group The acrylic resin is obtained by mixing with a crosslinking agent having an epoxy group, and contains an ester group having a reaction between the carboxyl group and the epoxy group. A decorative article, which is a decorative article arranged in the order of a resin-containing adherend, an adhesive layer, and a decorative layer, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the following formula (1) : The decorative article according to claim 1 or 2, wherein at least a part of the surface of the adherend is provided with a concave-convex surface of the concave portion and the convex portion, or a curved surface provided with a curved portion; the concave-convex surface or the curved surface is passed through the above The layer is followed by the decorative layer described above. The decorative article of claim 3, wherein the adhesive layer is contained in the uneven surface or the curved surface of the decorative layer via the adhesive layer. The decorative article of claim 1 or 2, wherein at least a part of the surface of the adherend contains a resin. The decorative article of claim 1 or 2, wherein the adhesive layer further contains a tackifier. The decorative article of claim 1 or 2, wherein the adhesive layer further contains a heat-resistant imparting agent. A method of manufacturing a decorative article, characterized by comprising: a step of preparing a resin-containing adherend; a step of preparing a decorative laminate having a decorative layer and an adhesive layer; and a step of bonding the adherend to the adhesive layer of the decorative layer laminate; wherein The adhesive layer is obtained by mixing an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group, and further comprising an ester group having a reaction between the carboxyl group and the epoxy group. A method for producing a decorative article, comprising: a step of preparing a resin-containing adherend; a step of preparing a decorative laminate having a decorative layer and an adhesive layer; and laminating the adherend with the decorative layer a step of laminating the above-mentioned adhesive layer of the body; wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the following formula (1): The method for producing a decorative article according to claim 8 or 9, wherein in the step of bonding the adherend to the adhesive layer of the laminate for the decorative layer, a heating operation, a pressurizing operation, and a decompression are performed. At least one of the operations. A decorative laminate comprising: a decorative layer and an adhesive layer disposed on the decorative layer, and a decorative layer for laminating the resin-containing adherend surface in the order of the adhesive layer and the decorative layer a body characterized in that the above-mentioned adhesive layer is composed of an acrylic resin having a carboxyl group and a crosslinking agent having an epoxy group. It is obtained by mixing and contains an ester group having a reaction of the above carboxyl group with the above epoxy group. A decorative laminated body comprising a decorative layer and a decorative laminated body which is subsequently laminated, wherein the adhesive layer contains an acrylic resin having a crosslinked structure of the following formula (1): The decorative laminate according to claim 11 or 12, wherein the adhesive layer further contains a tackifier. The decorative laminate according to claim 11 or 12, wherein the adhesive layer further contains a heat-resistant imparting agent.