JP2021107128A - Laminate - Google Patents

Abstract

To provide a laminate excellent in temporal adhesion between a support base material and a surface resin layer.SOLUTION: A laminate comprises: a support base material comprising leather; and a surface resin layer arranged in contact with the support base material, containing a polyacrylic urethane resin as a cured product of a resin composition which contains an acryl resin having a hydroxyl value of 40 mgKOH/g or more and 280 mgKOH/g or less and containing fluorine atoms, polyol which has a plurality of hydroxyl groups, and in which the hydroxyl groups interpose 6C or higher carbon chains, and polyfunctional isocyanate.SELECTED DRAWING: None

Description

The present invention relates to a laminate.

Conventionally, in various fields, surface protective resin members such as a surface protective film have been provided from the viewpoint of suppressing scratches on the surface. In recent years, a resin layer such as urethane resin is often used as a member for protecting the surface for scratch resistance.

For example, Patent Document 1 is a leather-like sheet in which a grain surface layer is laminated on the surface of a fiber base sheet, and the grain surface layer has a layer containing a shape-remembering polyurethane elastomer. The leather-like sheet to be used is disclosed.

Further, Patent Document 2 describes a synthetic resin leather in which a resin layer containing a thermoplastic polyurethane elastomer as a main component is laminated on at least one surface of a base material, and the resin component of the resin layer is a polycaprolactone-based thermoplastic polyurethane elastomer. A synthetic resin leather containing 80 to 95% by weight and 5 to 20% by weight of an acrylic soft resin is disclosed.

Further, Patent Document 3 describes a synthetic leather in which a skin layer made of a polyurethane resin and an antifouling layer are sequentially laminated on one surface of a fibrous base material, and the antifouling layer has a dry solid content. A synthetic leather comprising 25 to 45% by mass of a fluorine-based resin, 1 to 30% by mass of a silicone-based compound, and 3 to 20% by mass of a polyurethane resin is disclosed.

Further, Patent Document 4 provides a synthetic resin leather having high flexibility and good strength, abrasion resistance against repeated rubbing phenomenon, and chemical resistance against contact with a human body. For this purpose, a surface treatment agent obtained by cross-linking a mixture of polycarbonate urethane and ester urethane with carbodiimide is applied to the surface side of the film 1 containing vinyl chloride resin as a main component to provide flexibility, abrasion resistance and resistance. A leather on which a surface treatment layer 1a having excellent olein acidity is formed is disclosed.

Japanese Unexamined Patent Publication No. 2016-21129 Japanese Unexamined Patent Publication No. 2012-193481 Japanese Unexamined Patent Publication No. 2015-214773 International Publication No. 2014/109177

Since the surface of the leather is soft, if it is rubbed strongly with a sponge or a brush containing abrasive particles, scratches may occur and the appearance may be spoiled. Further, for the purpose of protecting from such scratches, a leather member laminated with a surface coating member made of a urethane layer is used, but in such a laminated body, the leather member has moisture permeability. Moisture may reach not only from the front side of the urethane layer but also from the back side (leather side). When moisture reaches the urethane layer from the leather side of the urethane layer, hydrolysis of the urethane layer is promoted, and the coat member may be peeled off over time.

The problem to be solved by the present invention is a laminate having a support base material made of leather and a surface resin layer arranged in contact with the support base material, and the polyacrylic urethane contained in the surface resin layer. The resin is an acrylic resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less and containing no fluorine atom, and a polyol having a plurality of reactive groups and having the reactive group via a carbon chain having 6 or more carbon atoms. It is an object of the present invention to provide a laminate having excellent adhesion over time between the supporting base material and the surface resin layer as compared with the case where the resin composition is composed of polyfunctional isocyanate and a cured product.

The above problem is solved by the following means.
<1>
A support base material made of leather and a surface resin layer arranged in contact with the support base material, which has a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, an acrylic resin containing a fluorine atom, and a plurality of hydroxyl groups. A laminate having a surface resin layer containing a polyacrylic urethane resin which is a cured product of a resin composition containing a polyol having a hydroxyl group having 6 or more carbon atoms via a carbon chain and a polyfunctional isocyanate. body.
<2>
Fluorine atom amount at the outermost surface of the surface resin layer [F _S] and the fluorine atom amount at the surface after 20 minutes etching with argon gas cluster ion gun 2mm square range output 5kV outermost surface [F The laminate according to <1>, wherein the ratio [(FI _-20 / F _{S ) × 100 (%)] of [I-20} ] and [(FI-20 / F S) × 100 (%)] is 2% or more and 50% or less.
<3>
The fluorine atom amount at the outermost surface of the surface resin layer _{[F S]} is less than 5 atm% or more 22 atm% <1> or laminate according to <2>.
<4>
The outermost fluorine atom amount at the outer surface _{[F S]} is laminated body according to at most 15 atm% or more 22atm% <3>.
<5>
The laminate according to any one of <1> to <4>, wherein the content of the fluorine atom in the polyacrylic urethane resin is 1.5% by mass or more and 8.0% by mass or less.
<6>
The resin composition has a molar ratio [OH _A / OH _P ] of 0.1 or more of the total amount of hydroxyl groups [OH _A ] in the acrylic resin and the total amount of hydroxyl groups [OH _{P] in the polyol.} 4. The laminate according to any one of <1> to <5>, which is 4 or less.
<7>
The laminate according to any one of <1> to <6>, wherein the surface resin layer has an average thickness of 10 μm or more and 100 μm or less.
<8>
The laminate according to any one of <1> to <7>, wherein the leather is at least one selected from the group consisting of polyurethane-based synthetic leather, vinyl chloride-based synthetic leather, and natural leather.
<9>
The resin composition contains a silicone resin having a plurality of functional groups that are reactive with isocyanate groups.
The fluorine atom amount at the outermost surface of the surface resin layer _{[F S]} is not more than 22 atm%, and the silicon atom content in the outermost surface _{[S S]} is less 2 atm% or more 6 atm%, of the outermost surface the ratio of the fluorine atom amount at the surface after etching for 1 minute with argon gas cluster ion gun output 5kV a range of 2mm square _{[F I-1]} and the _{[F S] [(F I} -1 / F S) _{× 100 (%)] is 0% or more and 70% or less, and the silicon atomic weight [SI-] on} the surface after etching the outermost surface 2 mm square area with an argon gas cluster ion gun having an output of 5 kV for 1 minute. _1] and the _{[S S]} and ratio _{[(S I-1 / S} S) × 100 (%)] is according to any one of <1> to <8> or less 70% 20% Laminated body.
<10>
The laminate according to <9>, wherein the silicone resin is a silicone resin having two functional groups in one molecular structure.
<11>
The silicone resin is set to <9> or <10> having at least one group selected from the group consisting of an amino group, a hydroxyalkyl group, a hydroxyl group, a carboxyl group, a silanol group and an epoxy group as the functional group. The laminate described.
<12>
The ratio [(FI _-1 / F _S ) × 100 (%)] of the cured product is 10% or more and 50% or less, and the ratio [(SI _-1 / S _S ) × 100 (%)] is The laminate according to any one of <9> to <11>, which is 30% or more and 60% or less.
<13>
After the ratio [(FI _-20 / F _S ) × 100 (%)] is 40% or less and the outermost surface 2 mm square is etched with an argon gas cluster ion gun having an output of 5 kV for 20 minutes. amount of silicon atoms _{[S I-20]} and the ratio of the _{[S S] [(S I} -20 / S S) × 100 (%)] is less than 40% 0% at the surface <9> - <12> The laminate according to any one of.
<14>
The laminate according to any one of <9> to <13>, wherein the content of the silicone resin is 0.1% by mass or more and 1% by mass or less with respect to the cured product.

According to the invention according to <1>, <7>, or <8>
A laminate having a support base material made of leather and a surface resin layer arranged in contact with the support base material, and the polyacrylic urethane resin contained in the surface resin layer has a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH. Resin composition consisting of an acrylic resin having a / g or less content and containing no fluorine atom, a polyol having a plurality of reactive groups and having the reactive group via a carbon chain having 6 or more carbon atoms, and a polyfunctional isocyanate. Provided is a laminate having excellent adhesion over time between the supporting base material and the surface resin layer as compared with the case where the product is a cured product.
According to the invention according to <2>
Fluorine atom amount at the outermost surface of the surface resin layer [F _S] and a fluorine atom amount at the surface after 20 minutes etching with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface [F _{I -20} ] and the ratio [(FI _-20 / F _S ) × 100 (%)] is less than 2% or more than 50%, and the adhesion between the supporting base material and the surface resin layer over time A laminate having excellent properties is provided.
According to the invention according to <3>
Fluorine atom amount at the outermost surface [F _S] is compared with the case where it is more than 5 atm% or less than 22 atm%, a laminate excellent in temporal adhesion between the supporting substrate and the surface resin layer is provided.
According to the invention according to <4>
Fluorine atom amount at the outermost surface [F _S] is compared with the case where it is more than 15 atm% or less than 22 atm%, a laminate excellent in temporal adhesion between the supporting substrate and the surface resin layer is provided.
According to the invention according to <5>
Compared with the case where the content of the fluorine atom in the polyacrylic urethane resin is less than 1.5% by mass or more than 8.0% by mass, the laminate having excellent adhesion between the supporting base material and the surface resin layer over time is obtained. Provided.
According to the invention according to <6>
In the resin composition, the molar ratio [OH _A / OH _P ] of the total amount of hydroxyl groups [OH _A ] in the acrylic resin and the total amount of hydroxyl groups [OH _P ] in the polyol is less than 0.1 or A laminate having excellent adhesion over time between the supporting base material and the surface resin layer is provided as compared with the case where the amount exceeds 4.
According to the invention according to <9>.
The surface resin layer
An acrylic resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, a polyol having a plurality of hydroxyl groups and having a hydroxyl group having 6 or more carbon atoms via a carbon chain, a polyfunctional isocyanate, and the like. When it is a cured product of a resin composition consisting of
With respect to an acrylic resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less and containing no fluorine atom, a polyol having a plurality of hydroxyl groups and having the hydroxyl group via a carbon chain having 6 or more carbon atoms, and an isocyanate group. In the case of a cured product of a resin composition composed of a silicone resin having a plurality of functional groups exhibiting reactivity and a polyfunctional isocyanate, or
With respect to an acrylic resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less and containing a fluorine atom, a polyol having a plurality of hydroxyl groups and having the hydroxyl group via a carbon chain having 6 or more carbon atoms, and an isocyanate group. Compared with the case of a cured product of a resin composition composed of a silicone resin having only one reactive functional group and a polyfunctional isocyanate, the surface layer's ability to follow the substrate of the surface layer with respect to shape changes (hereinafter referred to as “following”). A laminate having excellent "shape followability") is provided.
According to the invention according to <10>
A laminate having excellent shape followability is provided as compared with the case where the silicone resin is a silicone resin having one functional group in one molecular structure.
According to the invention according to <11>
A laminate having excellent shape followability is provided as compared with the case where the silicone resin is a silicone resin having an alkyl group or an aryl group as the functional group.
According to the invention according to <12>
When the ratio [(FI _-1 / F _S ) × 100 (%)] of the cured product is less than 10% or more than 50%, or the ratio [(SI _-1 / S _S ) × 100 (%)]. )] Is less than 30% or more than 60%, so that a laminate having excellent shape followability is provided.
According to the invention according to <13>
The ratio of the fluorine atom amount at the surface after 20 minutes etching with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface _{[F I-20]} and the with _{[F S] [(F I} -20 _{/ F S) × 100 (%} ) If] is greater than 40%, or a silicon atom of the surface after 20 minutes etching with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface [S _I-20] with the [compared with the case the ratio of _{S S] [(S I-} 20 / S S) × 100 where (%)] is greater than 40%, the laminate having excellent conformability is provided NS.
According to the invention according to <14>
Provided is a laminate having excellent shape followability as compared with the case where the content of the silicone resin is less than 0.1% by mass or more than 1% by mass with respect to the cured product.

Embodiments of the present invention will be described below. The present embodiment is an example of carrying out the present invention, and the present invention is not limited to the following embodiments.

<Laminated body>
The laminate according to the present embodiment includes a supporting base material made of leather (hereinafter, also simply referred to as “base material”) and a surface resin layer arranged in contact with the supporting base material (hereinafter, also simply referred to as “surface layer”). And have.
The surface resin layer has a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, and has an acrylic resin containing a fluorine atom (hereinafter, also simply referred to as “specific acrylic resin”) and a plurality of hydroxyl groups, and the hydroxyl groups are present. It contains a polyacrylic urethane resin which is a cured product of a resin composition containing a polyol (hereinafter, also simply referred to as “long chain polyol”) via a carbon chain having 6 or more carbon atoms and a polyfunctional isocyanate.

The laminate according to the present embodiment is excellent in adhesion over time between the supporting base material and the surface resin layer by satisfying the above-mentioned constitution.
The reason can be inferred as follows.

First, the surface layer in the present embodiment contains a polyacrylic urethane resin which is a polymer of a resin composition containing a specific acrylic resin (a), a long-chain polyol (b), and a polyfunctional isocyanate (c). In addition, this polymer is a urethane bond formed by reacting the OH group in the specific acrylic resin (a) and the OH group in the long chain polyol (b) with the isocyanate group in the polyfunctional isocyanate (c). -NHCOO-). That is, the specific acrylic resin (a) forms a crosslinked structure via the long-chain polyol (b) and the polyfunctional isocyanate (c). It is considered that the laminate according to the present embodiment is imparted with self-healing property by having the polyacrylic urethane resin having this structure. The self-healing property means that even if a scratch is generated on the surface due to contact with another substance (for example, rubbing), the scratch is repaired and restored to the original state or a state close to the original state. Point to.
The surface layer in the present embodiment has the above-mentioned polyacrylic urethane resin, and since this polyacrylic urethane resin has a fluorine atom in its structure, the surface layer is highly hydrophobic and the surface surface is high. It is difficult for water to permeate, which causes deterioration of the adhesion between the layer and the base material over time. Further, since the fluorine atom is bonded to the acrylic chain constituting the polyacrylic urethane resin and the fluorine atom is hard to be released, it is considered that the effect of suppressing the permeation of water is maintained for a long period of time.

(Ratio of fluorine atomic weight)
In the present embodiment, in the surface layer, a fluorine atom amount at the outermost surface and the [F _S], said argon gas cluster ion gun 20 min etched surface after the 2mm square range output 5kV outermost surface fluorine atom amount and _{[F I-20],} the ratio _{[(F I-20 / F} S) × 100 (%)] of preferably not more than 50% or 2%.

When the above ratio [FI _-20 / F _S × 100 (%)] is 2% or more and 50% or less, fluorine atoms are present at a high density on the outermost surface side of the surface layer, while the inside of the surface layer. Indicates that the fluorine atom has a low density. Therefore, by setting the above range, the influence of fluorine atoms at the interface with the base material is suppressed, and the adhesion between the surface layer and the base material is likely to be enhanced.
Further, in the surface layer of the present embodiment, when fluorine atoms are present at a high density on the outermost surface side as described above, the surface energy is reduced, and thereby the antifouling property is also enhanced.

The above ratio [(FI _-20 / F _S ) × 100 (%)] is more preferably 40% or less from the viewpoint of improving the adhesion between the base material and the surface layer over time. It is more preferably 30% or less, and more preferably 1% or more, further preferably 2% or more, from the viewpoint of antifouling property and the adhesiveness.

Further, in the present embodiment, in the surface layer, a fluorine atom amount at the outermost surface [F _S] and the surface after 40 minutes etching with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface fluorine atom amount at the _{[F I-40],} the ratio _{[(F I-40 / F} S) × 100 (%)] is preferably 50% or less than 2%, more than 40% 2% More preferably.

(Ratio of silicon atomic weight and ratio of fluorine atomic weight)
In the present embodiment, from the viewpoint of improving the shape followability, a fluorine atom amount at the outermost surface of the surface resin layer _{[F S]} is less 22 atm% (more preferably 12 atm% or more 22 atm% or less), and the outermost the silicon atom content at the surface [S _S] is less 2 atm% or more 6 atm%, the fluorine atom amount at the surface after etching for 1 minute with argon gas cluster ion gun 2mm square range output 5kV of the outermost surface [ F _I-1] and the _{[F S]} ratio of _{[(F I-1 / F} S) × 100 (%)] is 70% or less than 0%, and a 2mm square range of the outermost surface the ratio of the silicon atoms of the surface after etching for 1 minute with argon gas cluster ion gun output 5kV _{[S I-1]} and the _{[S S] [(S I} -1 / S S) × 100 (%) ] Is preferably 20% or more and 70% or less.

Further, the ratio _{[(F I-1 / F} S) × 100 (%)] in the cured product, from the viewpoint of improving the shape followability is preferably 10% to 50% or less, 10% or more 40 More preferably, it is% or less. From the same viewpoint, the ratio _{[(S I-1 / S} S) × 100 (%)] is preferably 60% or less than 30%, and more preferably 10% to 50%.

In the present embodiment, in the surface layer, in view of conformality, in the ratio _{[(F I-20 / F} S) × 100 (%)] 40% or less (more preferably 40% or more 0%) and wherein the ratio of the silicon atom content at the surface after 20 minutes etching with argon gas cluster ion gun 2mm square range output 5kV outermost surface [S _I-20] with the [S _S] [(S _{I-20 / S S) ×} 100 (%)] is preferably not less than 40% 0%.
From the same viewpoint, the ratio _{[(F I-20 / F} S) × 100 (%)] is 40% or less than 10%, and the argon gas cluster ion output 5kV a 2mm square range of the outermost surface the silicon atom content at the surface after 20 minutes etch with a gun _{[S I-20]} with the _{[S S]} ratio of _{[(S I-20 / S} S) × 100 (%)] 10% 50% The following is preferable.

The ratio _{[(F I-1 / F} S) × 100 (%)] a and the ratio _{[(S I-1 / S} S) × 100 (%)] to control the numerical range described above, for example the A silicone resin having a plurality of functional groups that is reactive with isocyanate groups is blended into the resin composition so as to be 0.1% by mass or more and 1% by mass or less with respect to the cured product of the resin composition. Can be achieved with.
Method of controlling the ratio _{[(S I-20 / S} S) × 100 (%)] and the ratio _{[(F I-20 / F} S) × 100 (%)] in the numerical range of the same is true.

Here, a method for measuring the atomic weight of fluorine and the atomic weight of silicon will be described.
Fluorine atomic weight is measured by XPS (X-ray photoelectron spectroscopy). Specifically, using an XPS analyzer (model: PHI5000 Versa Probe II) manufactured by ULVAC PHI Co., Ltd., the carbon atomic weight, oxygen atomic weight, nitrogen atomic weight, fluorine atomic weight, and silicon atomic weight can be measured by XPS under the following conditions. Each is measured, and the fluorine atomic weight (atm%) and the silicon atomic weight (atm%) with respect to the total atomic weight of these five elements are calculated, respectively.

-Measurement conditions-
X-ray source: Monochromatic AlKa
Output: 25W, 15kV
Detection area: 100 μmφ
Incident angle: 90 degrees Extraction angle: 45 degrees Charge neutralization: Neutralization gun condition 1.0V / ion gun 10V

Moreover, the etching method for the surface layer will be described.
Specifically, an area of 2 mm square on the outermost surface of the surface layer is etched with an argon gas cluster ion gun having an output of 5 kV.
-Etching conditions-
Etching gun: Argon gas cluster ion gun Acceleration voltage: 5kV
Sweep area: 2mm x 2mm
Rate: 5 nm / min (polyester equivalent)

In the present embodiment, in the surface layer, from the viewpoint of obtaining a high antifouling property, a fluorine atom amount at the outermost surface _{[F S],} is preferably from more than 5 atm% 22 atm%, more 15 atm% 22 atm% or less More preferably.

In the surface layer in the present embodiment, a fluorine atom amount [F _S] in this range can for example based on the total amount of polyacrylic urethane resin contained in the surface layer, a fluorine atom is 1.5 wt% 8.0 It can be achieved by blending so as to be less than mass%.
If the amount of fluorine atomic weight in the polyacrylic urethane resin exceeds 8.0% by mass, the hydrophobicity becomes too high, and the surface layer becomes non-uniform, which is not preferable. When the atomic weight of fluorine is smaller than 1.5% by mass, the amount of fluorine is too small, so that sufficient hydrophobicity cannot be obtained and hydrolysis is likely to occur.

Further, in order to obtain temporal adhesion between the substrate and the surface layer, the surface layer, a fluorine atom amount at the outermost surface and the [F _S], fluorine atom amount at the interface with the substrate [F _B] and , the ratio _{[F B / F S × 100} (%)] is preferably 40% or less 1% or more. Further, it is more preferably 1% or more and 35% or less, and further preferably 2% or more and 35% or less.

Here, the fluorine atom amount at the interface between the base material of the surface layer measurement method [F _B] will be described. Measurement of fluorine atoms of the interface [F _B] is carried out by measuring the cross section to prepare a slice having a slope.
First, a section having an inclination of an angle θ is prepared by a microtome from a laminate having a base material and a surface layer. The method described in JP-A-2004-219261 can be used to prepare the sections. At the slope in this section, the fluorine atomic weight at the interface between the substrate and the surface layer is measured by the method described above. The θ is an angle between 0.5 ° and 2 ° or less.

(How to achieve the ratio of fluorine atomic weight)
Next, a method of controlling the ratio [FI _-20 / F _S × 100 (%)] within the above range will be described. The ratio _{[F I-40 / F S} × 100 (%)], [F I-1 / F S × 100 (%)] and the ratio _{[F B / F S × 100} (%)] also, the following It can be controlled by the method.
The above-mentioned achievement method is not particularly limited, and examples thereof include the following methods.

Achievement method (1)
The polyacrylic urethane resin constituting the surface layer is a cured product of the specific acrylic resin (a), the long-chain polyol (b), and the polyfunctional isocyanate (c). Since the fluorine atom has low compatibility with the long-chain polyol (b) and the polyfunctional isocyanate (c), the specific acrylic resin (a) is likely to be oriented toward the outermost surface side of the surface layer, while the long chain The polyol (b) and the polyfunctional isocyanate (c) are likely to be oriented on the interface side with the base material. It is considered that this makes it easier to control the ratio [FI _-20 / F _S × 100 (%)] within the above range.

Achievement method (2)
Further, from the viewpoint of controlling the ratio [FI _-20 / F _S × 100 (%)] within the above range, the SP value (solubility parameter) of the resin contained in the base material is preferably 8.1 or more. By SP value of the resin in the substrate is 8.1 or more, the ratio reason [F I _/ F _S × 100 where (%)] is easily controlled in the above range is presumed as follows.
The higher the SP value of the resin, the larger the polar component in the molecular structure of the resin. The presence of this polar component facilitates the orientation of the long-chain polyol (b) and the polyfunctional isocyanate (c) toward the interface side with the base material, while the specific acrylic resin (a) is oriented toward the outermost surface side of the surface layer. It is thought that it will be easier to make.
Further, it is considered that the presence of the polar component in the base material binds to a functional group such as a hydroxyl group of the polyacrylic urethane resin, and the adhesion between the surface layer and the base material is further improved.

From the above viewpoint, the SP value (solubility parameter) of the resin contained in the base material is preferably 8.1 or more, more preferably 8.15 or more, and further preferably 8.2 or more. On the other hand, from the viewpoint of the stability of the base material, the upper limit of the SP value is preferably 20 or less, more preferably 18 or less, and further preferably 16 or less.

Examples of the resin having an SP value of 8.1 or more, that is, the resin containing a large amount of polar components in the molecular structure include polyester resin, polycarbonate resin, and polyacrylate resin. It is considered that by including at least one of these resins in the base material, the long-chain polyol (b) and the polyfunctional isocyanate (c) in the surface layer can be easily oriented toward the interface with the base material.

Here, a method of calculating the SP value of the resin will be described.
After analyzing the monomer composition of the resin by a known method, it is calculated by the Fedor method (specifically, the method described in Polymer. Eng. Sci., 14 [2] (1974)) using the following formula. NS.
SP value = (ΣΔei / ΣΔvi) ^1/2
Δei: Evaporative energy of an atom or atomic group Δvi: Molar volume of an atom or atomic group

Achievement method (3)
Further, as an achievement method, as the specific acrylic resin (a), a method of using an acrylic resin containing a fluorine atom in a side chain in the molecular structure of the resin can be mentioned.
It is considered that the fluorine atoms existing in the side chain of the specific acrylic resin (a) can move flexibly even in the surface layer, that is, the mobility of the side chain portion having the fluorine atoms is exposed on the outermost surface of the surface layer. Is considered to be equipped with. Therefore, the specific acrylic resin (a) is easily oriented toward the outermost surface side of the surface layer, while the long-chain polyol (b) and the polyfunctional isocyanate (c) are easily oriented toward the interface side with the base material. Conceivable.

Next, each member constituting the laminated body according to the present embodiment will be described in detail.

[Supporting base material]
The laminate according to the present embodiment has a supporting base material made of leather.

The leather may be either synthetic leather or natural leather, and may be subjected to various surface treatments. Examples of the leather include at least one selected from the group consisting of polyurethane-based synthetic leather, vinyl chloride-based synthetic leather, and natural leather.

(Physical characteristics of supporting base material)
The thickness (average thickness) of the base material is not particularly limited, but from the viewpoint of the strength of the laminated body, for example, 30 μm or more is preferable, 50 μm or more is more preferable, and 75 mm or more is further preferable.
The average thickness of the base material shall be the arithmetic mean of the thickness at 10 randomly selected base materials.

[Surface resin layer]
The laminate according to the present embodiment has a surface resin layer (surface layer) arranged in contact with the base material.

The surface layer preferably contains a polyacrylic urethane resin as a main component, and specifically, the content of the polyacrylic urethane resin with respect to the total amount of the surface layer is preferably 20% or more, preferably 30% or more. More preferably, it is more preferably 50% or more, and it may be 100%.

The polyacrylic urethane resin contained in the surface layer according to the present embodiment is obtained by polymerizing a resin composition containing at least a specific acrylic resin (a), a long-chain polyol (b), and a polyfunctional isocyanate (c).
Further, in the present embodiment, from the viewpoint of shape-following property, the resin composition further has a silicone resin having a plurality of functional groups exhibiting reactivity with an isocyanate group (hereinafter, "isocyanate group reactive silicone resin"). Also referred to as)).

(A) Specific Acrylic Resin In the present embodiment, a specific acrylic resin having a hydroxyl group (-OH) is used as the acrylic resin. The hydroxyl value of this specific acrylic resin is 40 mgKOH / g or more and 280 mgKOH / g or less.
Specific acrylic resins having a hydroxyl group include those having a carboxy group in addition to those having a hydroxyl group in the molecular structure.

The hydroxyl group is introduced, for example, by using a monomer having a hydroxyl group as a monomer as a raw material of a specific acrylic resin. Examples of the monomer having a hydroxyl group include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and N-methylol acrylicamine. , (1) Ethylene monomers having a hydroxyl group and the like.
Further, (2) an ethylenic monomer having a carboxy group such as (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, and maleic acid may be used.

Further, a monomer having no hydroxyl group may be used in combination with the monomer as a raw material of the specific acrylic resin. Monomers having no hydroxyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic. (Meta) acrylic acid alkyl esters such as n-butyl acid acid, isobutyl (meth) acrylic acid, 2-ethylhexyl (meth) acrylic acid, n-octyl (meth) acrylic acid, and n-dodecyl (meth) acrylic acid, etc. Examples thereof include ethylenic monomers that can be copolymerized with the monomers (1) and (2).

In addition, in this specification, "(meth) acrylic acid" means that both acrylic acid and methacrylic acid are included.

-Fluorine atom The specific acrylic resin has a fluorine atom in its molecular structure.
Fluorine atoms are introduced, for example, by using a monomer having a fluorine atom as a monomer that is a raw material of a specific acrylic resin. Examples of the monomer having a fluorine atom include 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, and perfluoro. Examples thereof include hexylethylene, hexafluoropropene, hexafluoropropene epoxiside, and perfluoro (propyl vinyl ether).

The fluorine atom is preferably contained in the side chain of the specific acrylic resin. Examples of the carbon number of the side chain containing a fluorine atom include those having 2 or more and 20 or less. The carbon chain in the side chain containing a fluorine atom may be linear or branched.
The number of fluorine atoms contained in one molecule of a monomer having a fluorine atom is not particularly limited, but is preferably 1 or more and 25 or less, and more preferably 3 or more and 17 or less.

The ratio of fluorine atoms to the entire specific acrylic resin is preferably 0.1% by mass or more and 50% by mass or less, and more preferably 1% by mass or more and 20% by mass or less.

-Hydroxy group value The hydroxyl value of the specific acrylic resin is 40 mgKOH / g or more and 280 mgKOH / g or less. The hydroxyl value is more preferably 70 mgKOH / g or more and 250 mgKOH / g or less.
When the hydroxyl value is 40 mgKOH / g or more, the polyacrylic urethane resin having a high crosslink density is polymerized, the permeation of pollutants into the surface layer is suppressed, and excellent antifouling property can be obtained. On the other hand, when the amount is 280 mgKOH / g or less, a polyacrylic urethane resin having appropriate flexibility can be obtained, the viscosity of the solution in which the specific acrylic resin is dissolved is reduced, and the surface layer is excellent in formability.
The hydroxyl value of the specific acrylic resin is adjusted by the ratio of the monomer having a hydroxyl group in all the monomers for synthesizing the specific acrylic resin.

The hydroxyl value represents the number of mg of potassium hydroxide required for acetylating a hydroxyl group (hydroxyl group) in 1 g of a sample. The hydroxyl value in this embodiment is measured according to the method (potentiometric titration method) defined in JIS K0070 (1992). However, if the sample does not dissolve, a solvent such as dioxane or tetrahydrofuran (THF) is used as the solvent.

The specific acrylic resin is synthesized, for example, by mixing the above-mentioned monomers, performing ordinary radical polymerization, ionic polymerization, or the like, and then purifying the specific acrylic resin.

(B) Long-chain polyol A long-chain polyol is a carbon chain having a plurality of hydroxyl groups (-OH) and having 6 or more carbon atoms (the number of carbon atoms in the linear portion connecting the hydroxyl groups). It is a polyol via. That is, a long-chain polyol is a polyol in which all hydroxyl groups are linked by carbon chains having 6 or more carbon atoms (the number of carbon atoms in the linear portion connecting the hydroxyl groups).

The number of functional groups (that is, the number of hydroxyl groups contained in one molecule of the long-chain polyol) of the long-chain polyol may be, for example, in the range of 2 or more and 5 or less, and may be 2 or more and 3 or less.

A carbon chain having 6 or more carbon atoms in a long-chain polyol represents a chain having 6 or more carbon atoms in a linear portion connecting hydroxyl groups. As the carbon chain having 6 or more carbon atoms, one selected from an alkylene group or one or more alkylene groups and -O-, -C (= O)-, and -C (= O) -O-. A divalent group formed by combining the above groups can be mentioned. The long-chain polyol having a hydroxyl group via a carbon chain having 6 or more carbon atoms is − [CO (CH ₂ ) _n1 O] _n2 −H (where n1 is 1 or more and 10 or less (preferably 3 or more and 6 or less, more preferably). 5), and n2 preferably has a structure of 1 or more and 50 or less (preferably 1 or more and 35 or less, more preferably 1 or more and 10 or less, still more preferably 2 or more and 6 or less).

Examples of the long-chain polyol include bifunctional polycaprolactone diol, trifunctional polycaprolactone triol, and tetrafunctional or higher functional polycaprolactone polyol.

As the bifunctional polycaprolactone diol, for example, − [CO (CH ₂ ) _n11 O] _n12 −H (where n11 represents 1 or more and 10 or less (preferably 3 or more and 6 or less, more preferably 5), n12 represents. Examples thereof include a compound having two groups having a hydroxyl group at the terminal, which is represented by 1 or more and 50 or less (preferably 3 or more and 35 or less). Of these, the compound represented by the following general formula (1) is preferable.

(In the general formula (1), R represents an alkylene group or a divalent group formed by combining an alkylene group with one or more groups selected from −O− and −C (= O) −. m and n each independently represent an integer of 1 or more and 35 or less.)

In the general formula (1), the alkylene group contained in the divalent group represented by R may be linear or branched. As the alkylene group, for example, an alkylene group having 1 or more and 10 or less carbon atoms is preferable, and an alkylene group having 1 or more and 5 or less carbon atoms is more preferable.
As the divalent group represented by R, a linear or branched alkylene group having 1 or more and 10 or less carbon atoms (preferably 2 or more and 5 or less carbon atoms) is preferable, and 1 or more and 5 or less carbon atoms. A group consisting of two linear or branched alkylene groups (preferably having 1 to 3 carbon atoms) linked by -O- or -C (= O)-(preferably -O-) is preferable. .. Among _{these, * - C 2 H 4 -} *, * - C 2 H 4 OC 2 H 4 - *, or _{* -C (CH 3) 2 -} (CH 2) 2 - * a divalent represented Groups are more preferred. The divalent groups listed above are bound at the "*" portion.
m and n each independently represent an integer of 1 or more and 35 or less, preferably 2 or more and 10 or less, and more preferably 2 or more and 5 or less.

As the trifunctional polycaprolactone triol, for example,-[CO (CH ₂ ) _n21 O] _n22- H (where n21 represents 1 or more and 10 or less (preferably 3 or more and 6 or less, more preferably 5)), and n22 represents. Examples thereof include compounds having three groups having a hydroxyl group at the terminal, which are represented by 1 or more and 50 or less (preferably 1 or more and 28 or less). Of these, the compound represented by the following general formula (2) is preferable.

(In the general formula (2), R is a trivalent group obtained by removing one hydrogen atom from an alkylene group, or a trivalent group obtained by removing one hydrogen atom from an alkylene group, and an alkylene group, —O—, and It represents a trivalent group consisting of a combination of one or more groups selected from −C (= O) −. L, m, and n each independently represent an integer of 1 or more and 28 or less, and l + m + n is 3. More than 30 or less.)

In the general formula (2), when R represents a trivalent group obtained by removing one hydrogen atom from an alkylene group, the group may be linear or branched. As the trivalent group obtained by removing one hydrogen atom from the alkylene group, for example, an alkylene group having 1 or more and 10 or less carbon atoms is preferable, and an alkylene group having 1 or more and 6 or less carbon atoms is more preferable.
Further, R is a trivalent group obtained by removing one hydrogen atom from the alkylene group shown above, an alkylene group (for example, an alkylene group having 1 to 10 carbon atoms), -O-, and -C (= O). It may be a trivalent group formed by combining one or more groups selected from −.
The trivalent group represented by R is a trivalent group obtained by removing one hydrogen atom from a linear or branched alkylene group having 1 or more and 10 or less carbon atoms (preferably 3 or more and 6 or less carbon atoms). Group is preferred. Among these, * _{-CH 2-} CH (-*) -CH _2- *, CH _3- C (-*) (-*)-(CH ₂ ) _2- *, CH ₃ CH ₂ C (-*) _{(- *) (CH 2)} 3 - * 3 -valent group represented by is more preferable. The trivalent groups listed above are bound at the "*" portion.
l, m, and n each independently represent an integer of 1 or more and 28 or less, preferably 2 or more and 10 or less, and more preferably 2 or more and 5 or less. l + m + n is 3 or more and 30 or less, preferably 6 or more and 30 or less, and more preferably 6 or more and 20 or less.

As the long-chain polyol, only one type may be used, or two or more types may be used in combination.

The molar ratio [OH _A / OH _{P ] of the amount of total hydroxyl groups [OH A} ] contained in the specific acrylic resin (a) and the amount of _{total hydroxyl groups [OH P} ] contained in the long-chain polyol (b) is 0. It is preferably 1 or more and 4 or less, more preferably 0.15 or more and 3 or less, and further preferably 0.25 or more and 2 or less.
When the molar ratio [OH _A / OH _P ] is 0.1 or more and 4 or less, the amount of the specific acrylic resin (a) which is a hard segment and the amount of the long chain polyol (b) which is a soft segment are in harmony. It is enhanced and the self-healing property of the surface layer is easily enhanced.

As the long-chain polyol, those having a hydroxyl value of 30 mgKOH / g or more and 300 mgKOH / g or less are preferably used, and 50 mgKOH / g or more and 250 mgKOH / g or less are more preferable. When the hydroxyl value is 30 mgKOH / g or more, the urethane resin having a high crosslink density is polymerized, while when it is 300 mgKOH / g or less, a urethane resin having appropriate flexibility can be easily obtained.

The hydroxyl value represents the number of mg of potassium hydroxide required for acetylating a hydroxyl group (hydroxyl group) in 1 g of a sample. The hydroxyl value in the present embodiment is measured according to the method (potentiometric titration method) defined in JIS K0070 (1992). However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

(C) Polyfunctional isocyanate The polyfunctional isocyanate (c) is a compound having a plurality of isocyanate groups (-NCO), and includes, for example, a hydroxyl group possessed by the specific acrylic resin (a), a hydroxyl group possessed by a long-chain polyol (b), and the like. It reacts to form a urethane bond (-NHCOO-). Then, it functions as a cross-linking agent for cross-linking the specific acrylic resin (a) with each other, the specific acrylic resin (a) with the long-chain polyol (b), and the long-chain polyol (b) with each other.

The polyfunctional isocyanate is not particularly limited, and examples thereof include bifunctional diisocyanates such as methylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Further, a polyfunctional isocyanate which is a multimer of hexamethylene polyisocyanate and has a burette structure, an isocyanurate structure, an adduct structure, an elastic structure and the like is also preferably used.
A commercially available product may be used as the polyfunctional isocyanate, and examples thereof include polyisocyanate (duranate) manufactured by Asahi Kasei Corporation.
Only one type of polyfunctional isocyanate may be used, or two or more types may be mixed and used.

As for the amount of polyfunctional isocyanate, the ratio of isocyanate groups (-NCO) to the total amount of hydroxyl groups (-OH) in the specific acrylic resin (a) and long-chain polyol (b) is 0.8 in terms of molar ratio. The amount is preferably adjusted to 1.6 or more, and more preferably 1 or more and 1.3 or less in terms of molar ratio.
When the amount of the polyfunctional isocyanate is 0.8 or more in the molar ratio, the urethane resin having a high crosslink density is polymerized, and the self-healing property of the formed surface layer can be easily enhanced. On the other hand, when the amount of the polyfunctional isocyanate is 1.6 or less in the above molar ratio, it becomes easy to obtain a urethane resin having appropriate elasticity.

(D) Isocyanate Group Reactive Silicone Resin In this embodiment, a silicone resin having a plurality of functional groups exhibiting reactivity with an isocyanate group (isocyanate group reactive silicone resin) is used.
By reacting the specific acrylic resin (a) with the isocyanate group-reactive silicone resin (d) via the polyfunctional isocyanate (c), a siloxane bond is introduced into the side chain of the specific acrylic resin (a) and formed. The coefficient of friction of the surface layer is reduced.

As a functional group having an isocyanate group-reactive silicone resin that is reactive with an isocyanate group, for example, the amino group (-N (-R ¹¹ ) ( ^{-R 12} ) / R ¹¹ and R ¹² are independent of each other. Hydrogen atom or alkyl group having 1 or more and 3 or less carbon atoms), hydroxyalkyl group (-R ^21- OH / R ²¹ represents an alkylene group having 1 or more and 10 or less carbon atoms), hydroxyl group (-OH), Examples thereof include a carboxyl group (-COOH), a silanol group (-SiOH), and an epoxy group.
Among these, a hydroxyalkyl group or a hydroxyl group is preferable.
The isocyanate group-reactive silicone resin may have two or more of the functional groups in one molecular structure.

The number of the functional groups contained in one molecular structure of the isocyanate group-reactive silicone resin is not particularly limited as long as it has two or more kinds. However, it is more preferable that the silicone resin has two functional groups in one molecular structure. Since the number of the functional groups contained in one molecular structure is two, there are two places where the isocyanate group-reactive silicone resin is bonded and fixed to the specific acrylic resin. Therefore, the mobility of the chain having a siloxane bond is further improved, the portion having a silicon atom is more easily exposed on the surface of the surface layer, and the friction coefficient of the surface layer is more easily reduced.
When two of the functional groups are contained in one molecular structure, the position of the functional groups should be at the ends (both ends) of the main chain of the silicone resin from the viewpoint of making it easier to reduce the friction coefficient of the surface layer. Is more preferable.

Examples of the isocyanate group-reactive silicone resin include compounds having the functional groups at at least both ends of the main chain of the silicone resin, and specific examples thereof include compounds having a structure represented by the following general formula (P1). Be done.
As the isocyanate group-reactive silicone resin, a compound having a structure represented by the following general formula (P1) is more preferable.

In the general formula (P1), X ¹¹ and X ¹² are functional groups independently reactive with an isocyanate group, and R ³¹ is a hydrogen atom, an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group or an isocyanate. A functional group exhibiting reactivity with respect to a group, and m1 represents an integer of 1 or more. Incidentally, R ³¹ there are a plurality in the general formula (P1) may each be the same or different.

In the general formula (P1), the ^{alkyl group represented by R 31} may be linear, branched, or cyclic. The number of carbon atoms of the alkyl group is preferably 1 or more and 8 or less, and more preferably 1 or more and 3 or less. Examples of the alkyl group include a methyl group, an ethyl group, a butyl group and the like, and a methyl group is preferable.

The ^{aryl group represented by R 31} preferably has 4 or more and 20 or less carbon atoms. Examples of the aryl group include a phenyl group, a toluyl group, a naphthyl group and the like, and a phenyl group is preferable.

The R ³¹ is preferably a hydrogen atom, a methyl group, an ethyl group, or a phenyl group independently, and more preferably a methyl group. R ³¹ is more present in the general formula (P1) may each be the same or different, but preferably all the same.

Although m1 is not particularly limited, for example, 3 or more and 1000 or less can be mentioned.

The compound having the structure represented by the general formula (P1) preferably has the above-mentioned functional group only in ^{X 1} and R ^32.

Examples of the weight average molecular weight of the isocyanate group-reactive silicone resin include 250 or more and 50,000 or less, and may be 500 or more and 20,000 or less.

-Other additives-
The surface layer according to the present embodiment may further contain other additives. For example, as another additive, the reaction between the hydroxyl group (-OH) in the antistatic agent, the specific acrylic resin (a) and the long-chain polyol (b) and the isocyanate group (-NCO) in the polyfunctional isocyanate (c) is carried out. Examples thereof include a reaction accelerator for promoting the reaction.

-Antistatic agents Specific examples of antistatic agents include cationic surfactants (for example, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylamine hydrochlorides, imidazolium salts, etc.), and anionic surfactants. (For example, alkyl sulfonate, alkyl benzene sulfonate, alkyl phosphate, etc.), non-ionic surfactant compounds (eg, glycerin fatty acid ester, polyoxyalkylene ether, polyoxyethylene alkyl phenyl ether, N, N-bis-2) -Hydroxyethyl alkylamine, hydroxyalkyl monoethanolamine, polyoxyethylene alkylamine, fatty acid diethanolamide, polyoxyethylene alkylamine fatty acid ester, etc.), amphoteric surfactant compounds (eg, alkylbetaine, alkylimidazolium betaine, etc.), etc. Can be mentioned.

Moreover, as an antistatic agent, the thing containing quaternary ammonium can be mentioned.
Specifically, tri-n-butylmethylammonium bistrifluoromethanesulfonimide, lauryltrimethylammonium chloride, octyldimethylethylammonium ethyl sulfate, didecyldimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylhydroxyethylammonium paratoluene Examples thereof include phonate, tributylbenzylammonium chloride, lauryldimethylaminoacetate betaine, lauric acid amide propyl betaine, octanoate amide propyl betaine, and hydrochloride of polyoxyethylene stearylamine. Among these, tri-n-butylmethylammonium bistrifluoromethanesulfonimide is preferable.

Further, a high molecular weight antistatic agent may be used.
Examples of the high molecular weight antistatic agent include polymer compounds obtained by polymerizing a quaternary ammonium base-containing acrylate, polystyrene sulfonic acid type polymer compounds, polycarboxylic acid type polymer compounds, polyether ester type polymer compounds, and ethylene oxide-. Examples thereof include epichlorohydrin type polymer compounds and polyether ester amide type polymer compounds.

Examples of the polymer compound obtained by polymerizing the quaternary ammonium base-containing acrylate include a polymer compound having at least the following structural unit (A).

(In the structural unit (A), R ¹ represents a hydrogen atom or a methyl group, R ² , R ³ and R ⁴ each independently represent an alkyl group, and X ⁻ represents an anion.)

The polymerization of the high molecular weight antistatic agent can be carried out by a known method.
As the high molecular weight antistatic agent, only the polymer compound composed of the same polymerizable monomer may be used, or two or more kinds of polymer compounds composed of different polymerizable monomers may be used in combination.

In the present embodiment, the surface resistance of the formed surface layer ^{is preferably adjusted to be in the range of 1 × 10 9} Ω / □ or more and 1 × 10 ¹⁴ Ω / □ or less, and the volume resistance is 1 × 10. It is preferable to adjust so that the range is ⁸ Ωcm or more and 1 × 10 ^{13 Ωcm or less.}
Surface resistance and volume resistance are measured according to JIS-K6911 in an environment of 22 ° C. and 55% RH using a Hiresta UPMCP-450 type UR probe manufactured by Dia Instruments Co., Ltd.
If the antistatic agent is contained, the surface resistance and volume resistance of the surface layer are controlled by adjusting the type and content of the antistatic agent.

The antistatic agent may be used alone or in combination of two or more.

-Reaction accelerator As a reaction accelerator that promotes the reaction between the hydroxyl group (-OH) in the specific acrylic resin (a) and the long-chain polyol (b) and the isocyanate group (-NCO) in the polyfunctional isocyanate (c), For example, there are metal catalysts of tin and bismuth. For example, there are Neostan U-28, U-50, U-600 and tin stearate (II) of Nitto Kasei Co., Ltd. In addition, XC-C277, XK-640, etc. of Kusumoto Kasei Co., Ltd. can be mentioned.

-Formation of surface resin layer-
The method for forming the surface layer in the laminate according to the present embodiment is not particularly limited. For example, it can be formed by polymerizing and curing a resin composition for forming a surface layer containing a specific acrylic resin (a), a long-chain polyol (b), and a polyfunctional isocyanate (c).

As an example of the method for forming the surface layer, for example, it has a first solution containing a specific acrylic resin (a) and a long-chain polyol (b), and a second solution containing a polyfunctional isocyanate (c). A solution set for surface layer formation is used. The first solution and the second solution are mixed and applied on a substrate to form a coating film. Then, the surface layer can be formed by heating and curing.

-Physical characteristics of the surface layer-
-Thickness The thickness (average thickness) of the surface layer is not particularly limited, but is preferably, for example, 10 μm or more and 100 μm or less, more preferably 12.5 μm or more and 80 μm or less, and 15 μm or more and 75 μm or less. Is even more preferable.
When the thickness of the surface layer is 10 μm or more, the height difference due to the roughness of the surface of the base material is sufficiently filled by the surface layer, and the surface of the laminate (that is, the outermost surface on the surface layer side) Smoothness can be improved. On the other hand, when the thickness of the surface layer is 100 μm or less, the formability of the surface layer is excellent.

[Adhesive layer]
The laminate according to the present embodiment may include a base material and a layer other than the surface layer. For example, it may have an adhesive layer arranged on a surface of the base material that does not have a surface layer.
The adhesive layer is, for example, a layer provided for the purpose of attaching the laminated body to the surface of another member. The adhesive layer is not particularly limited, and a known adhesive tape, adhesive film, or the like can be used.

[Use]
Since the laminate of the present embodiment has the above structure, it has self-healing properties and is excellent in adhesion between the base material and the surface layer over time. Therefore, the laminate of the present embodiment has various uses, for example, automobile interior parts, railroad vehicle interior parts, aircraft interior parts, motorcycle seats, bicycle seats, furniture (for example, sofas, etc.), bags (for example, sofas, etc.). For example, bags, land cells, etc.), footwear, shoes, leather accessories (wallets, coin cases, key cases, pass cases, key chains, etc.), interior and exterior materials for building, clothing exterior and lining, wall coverings, flooring, tiles, etc. Can be suitably used for.
In addition, in portable devices (for example, mobile phones, portable game machines, etc.), bodies other than screens, building materials, storage containers (for example, suitcases, etc.), cosmetic containers, glasses (for example, frames, etc.), sports equipment (for example, frames, etc.) Examples include golf clubs, rackets, etc.), writing tools (eg fountain pens, etc.), stationery (pencil cases, etc.), clothing storage tools (eg, hangers, etc.), leather modified products, and modified members.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, "part" is based on mass unless otherwise specified.

[Example 1]
<Synthesis of acrylic resin prepolymer A1>
2 each polymerizable monomer of n-butyl methacrylate (nBMA), hydroxyethyl methacrylate (HEMA), and an acrylic monomer containing a fluorine atom (having a perfluorohexyl group; FAMAC6, manufactured by Unimatec Co., Ltd.) The mixture was mixed at a molar ratio of .5: 3.0: 0.5. Further, a polymerization initiator (azobisisobutyronitrile (AIBN)) having a ratio of 2% by mass of the polymerizable monomer and methyl ethyl ketone (MEK) having a ratio of 40% by mass of the polymerizable monomer are added to make the polymer polymerizable. A monomeric solution was prepared.
This polymerizable monomer solution was placed in a dropping funnel, and was dropped over 3 hours under stirring in MEK having a temperature of 80 ° C. and a ratio of the polymerizable monomer to 50% by mass under nitrogen reflux to polymerize. Further, a liquid composed of MEK having a ratio of 10% by mass of the polymerizable monomer and AIBN having a ratio of 0.5% by mass of the polymerizable monomer was added dropwise over 1 hour to complete the reaction. During the reaction, the temperature was maintained at 80 ° C. and stirring was continued. In this way, the acrylic resin prepolymer A1 was synthesized.
When the hydroxyl value of the obtained acrylic resin prepolymer A1 was measured according to the method (potentiometric titration method) defined in JIS K0070-1992, the hydroxyl value was 175 mgKOH / g.
Moreover, when the weight average molecular weight of the acrylic resin prepolymer A1 was measured by the above-mentioned method using gel permeation chromatography (GPC), the weight average molecular weight was 17,000.

<Preparation of surface layer forming liquid (polymer 1)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A1 liquid (solid content 50% by mass): 42 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 38 parts -Methyl ethyl ketone: 20 parts The ratio of the total hydroxyl groups of the acrylic resin prepolymer A1 and the long-chain polyol (molecular ratio [OH _A / OH _P ]) was 0.5.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 40 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface layer forming liquid (polymer 1).

<Formation of laminated body (1)>
As the base material 1, a cowhide black chrome tanned skin (manufactured by Token Co., Ltd.) having a thickness of 1 mm was prepared.
The surface layer forming liquid (polymer 1) was applied onto the substrate with a wire bar and then cured at 80 ° C. for 1 hour to form a surface layer. The thickness of the surface layer was 30 μm. In this way, the laminated body (1) was obtained.

[Example 2]
In the preparation of the first solution in the preparation of the surface layer forming liquid (polymer 1) in Example 1, the acrylic resin prepolymer A1 liquid (solid content 50% by mass) and the long-chain polyol (polycaprolactone triol, praxel 308, ( For (manufactured by Daicel Co., Ltd.), the mass ratio of the two is changed without changing the total amount, and the ratio of the total hydroxyl groups of the two (molar ratio [OH _A / OH _P ]) is 1 . A surface layer forming liquid (polymer 2) was prepared in the same manner as in Example 1 except that the value was adjusted to 0, and a laminate (2) was further obtained.

[Example 3]
The acrylic resin prepolymer A1 used in Example 1 was changed to a mixture of the acrylic resin prepolymer A1 and the following acrylic resin prepolymer A2 having no fluorine atom, and further, a surface layer forming liquid having the following composition (polymer 3) was changed. ) Was prepared, and a laminate (3) was obtained in the same manner as in Example 1.

<Synthesis of acrylic resin prepolymer A2>
In the synthesis of the acrylic resin prepolymer A1 of Example 1, an acrylic monomer containing a fluorine atom (FAMAC6, manufactured by Unimatec Co., Ltd.) was not used, and n-butyl methacrylate (nBMA) and hydroxyethyl methacrylate (HEMA) were used. Acrylic resin prepolymer A2 was synthesized in the same manner as acrylic resin prepolymer A1 except that the polymerizable monomer was mixed in a ratio of 3.4: 2.6 mol to synthesize a prepolymer.
The hydroxyl value of the obtained acrylic resin prepolymer A2 was 175 mgKOH / g. The weight average molecular weight of the acrylic resin prepolymer A1 was 16000.

<Preparation of surface layer forming liquid (polymer 3)>
After mixing and stirring the following components, a first solution was prepared.
・ Acrylic resin prepolymer A1 liquid (solid content 50% by mass): 28 parts ・ Acrylic resin prepolymer A2 liquid (solid content 50% by mass): 12 parts ・ Long-chain polyol (polycaprolactone triol, Praxel 308, Daicel Co., Ltd. Manufactured by the same company, molecular weight 850, hydroxyl value 190-200 mgKOH / g): 41 parts ・ Methyl ethyl ketone: 20 parts The ratio of the amount of total hydroxyl groups between the acrylic resin prepolymer A1 and the long-chain polyol (molar ratio [OH _A / OH _P] ]) Was 0.4.

[Example 4]
In the preparation of the first solution in the preparation of the surface layer forming liquid (polymer 1) in Example 1, the acrylic resin prepolymer A1 liquid (solid content 50% by mass) and the long-chain polyol (polycaprolactone triol, praxel 308, ( (Manufactured by Daicel Co., Ltd.), the mass ratio of the two was changed without changing the total amount, and the ratio of the total hydroxyl groups of the two (molar ratio [OH _A / OH _P ]) was adjusted to 2.0. Except for the above, a surface layer forming solution (polymer 4) was prepared in the same manner as in Example 1, and a laminate (4) was further obtained.

[Example 5]
<Synthesis of acrylic resin prepolymer A3>
4 each polymerizable monomer of n-butyl methacrylate (nBMA), hydroxyethyl methacrylate (HEMA), and an acrylic monomer containing a fluorine atom (having a perfluorohexyl group; FAMAC6, manufactured by Unimatec Co., Ltd.) Acrylic resin prepolymer A3 was synthesized in the same manner as acrylic resin prepolymer A1 except for the molar ratio of 1: 1.0: 1.0.
Moreover, when the hydroxyl value of the obtained acrylic resin prepolymer A3 was measured according to the method (potentiometric titration method) defined in JIS K0070-1992, the hydroxyl value was 44 mgKOH / g.

<Preparation of surface protection member forming liquid (polymer 5)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A2 liquid (solid content 50% by mass): 80 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 40 parts -Methyl ethyl ketone: 20 parts The ratio of the total hydroxyl groups of the acrylic resin prepolymer A11 and the long-chain polyol (molecular ratio [OH _A / OH _P ]) was 1.0.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 40 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface protection member forming liquid (polymer 5).

<Formation of laminated film (5)>
A laminated film (5) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 5) was used instead of the surface protective member forming liquid (polymer 1).

[Example 6]
<Synthesis of acrylic resin prepolymer A4>
1 each polymerizable monomer of n-butyl methacrylate (nBMA), hydroxyethyl methacrylate (HEMA), and an acrylic monomer containing a fluorine atom (having a perfluorohexyl group; FAMAC6, manufactured by Unimatec Co., Ltd.) Acrylic resin prepolymer A4 was synthesized in the same manner as acrylic resin prepolymer A1 except for the molar ratio of .6: 4.2: 0.2.
Moreover, when the hydroxyl value of the obtained acrylic resin prepolymer A11 was measured according to the method (potentiometric titration method) defined in JIS K0070-1992, the hydroxyl value was 268 mgKOH / g.

<Preparation of surface protection member forming liquid (polymer 6)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A4 solution (solid content 50% by mass): 52 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 40 parts -Methyl ethyl ketone: 20 parts The ratio of the total hydroxyl groups of the acrylic resin prepolymer A11 and the long-chain polyol (molecular ratio [OH _A / OH _P ]) was 1.0.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 40 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface protection member forming liquid (polymer 6).

<Formation of laminated film (6)>
A laminated film (6) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 6) was used instead of the surface protective member forming liquid (polymer 1).

[Example 7]
<Synthesis of acrylic resin prepolymer A5>
2 each polymerizable monomer of n-butyl methacrylate (nBMA), hydroxyethyl methacrylate (HEMA), and an acrylic monomer containing a fluorine atom (having a perfluorohexyl group; FAMAC6, manufactured by Unimatec Co., Ltd.) Acrylic resin prepolymer A5 was synthesized in the same manner as acrylic resin prepolymer A1 except for the molar ratio of .8: 3.0: 0.2.
Moreover, when the hydroxyl value of the obtained acrylic resin prepolymer A5 was measured according to the method (potentiometric titration method) defined in JIS K0070-1992, the hydroxyl value was 190 mgKOH / g.

<Preparation of surface protection member forming liquid (polymer 7)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A5 liquid (solid content 50% by mass): 42 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 38 parts -Methyl ethyl ketone: 20 parts The ratio of the total hydroxyl groups of the acrylic resin prepolymer A11 and the long-chain polyol (molecular ratio [OH _A / OH _P ]) was 0.5.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 40 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface protection member forming liquid (polymer 7).

<Formation of laminated film (7)>
A laminated film (7) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 7) was used instead of the surface protective member forming liquid (polymer 1).

[Comparative Example 1]
In Example 1, a member (C1) having no surface layer formed on the base material 1 (cowhide black chrome tanned skin), that is, the base material 1 as it was was obtained.

[Comparative Example 2]
Instead of the acrylic resin prepolymer A1 used in Example 1, the above-mentioned acrylic resin prepolymer A2 having no fluorine atom was changed, and a surface layer forming liquid (polymer 8) having the following composition was prepared. A laminate (C2) was obtained in the same manner as in Example 1.

<Preparation of surface layer forming liquid (polymer 8)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A2 liquid (solid content 50% by mass): 40 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 41 parts -Methyl ethyl ketone: 20 parts The ratio of the total hydroxyl groups of the acrylic resin prepolymer A1 and the long-chain polyol (molecular ratio [OH _A / OH _P ]) was 0.5.

[Measurement of physical properties]
Fluorine atom amount at the outermost surface of the surface layer [F _S], fluorine atom amount at the surface after 20 minutes etching with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface [F _{I-20] The fluorine atomic weight [FI-40} ] on the outermost surface after etching a 2 mm square area with an argon gas cluster ion gun having an output of 5 kV for 40 minutes was measured by the above-mentioned methods.
The results are shown in Table 1.

[evaluation]
The following evaluations were performed on the laminates or members obtained in each example. The results are shown in Table 1.

-Evaluation of adhesion after leaving for 3 months-
The laminate or member obtained in each example was left in an environment of 50 ° C. and 98 RH% for 3 months. A cross-cut test was conducted according to JISK5600-5-6 (1999), and the adhesion between the base material and the surface layer over time was evaluated according to the following evaluation criteria.
A (○): The surface did not change when the cellophane tape was peeled off B (△): The surface was partially peeled off when the cellophane tape was peeled off C (×): The cellophane tape was peeled off The surface is completely peeled off when peeled off

-Evaluation of scratch resistance-
After rubbing the surface (however, the surface on which the surface layer is formed is the surface on the side where the surface layer is formed) with a scrubbing brush (Scotch-Brite, manufactured by 3M Ltd.) 10 times under a ^{load of 100 g / cm 2.} After storing at room temperature for 24 hours, the presence or absence of surface scratches was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria A (○): No scratches B (△): Minor scratches are confirmed depending on the angle C (×): Scratched

-Evaluation of hydrolyzability-
A 1% sodium hydroxide solution was soaked in absorbent cotton, and the mixture was brought into close contact with the surface of the laminate or member obtained in each example, and allowed to stand at 55 ° C. for 24 hours. After removing the cotton wool, washing with pure water and drying, the surface condition was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria A (○): No change B (△): Discolored C (×): Surface peeled off

As shown in Table 1, the laminates obtained in each example are superior in adhesion and hydrolyzability after being left for 3 months as compared with those of the comparative example, so that the supporting base material and the surface resin layer are excellent. It can be said that a product having excellent adhesion with time over time has been obtained.

[Example B1]
<Preparation of surface layer forming liquid (polymer B1)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A1 liquid (solid content 50% by mass): 30 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 29 parts -Both end-modified silicone resin having hydroxyl groups (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 0.5 parts The amount of total hydroxyl groups of the acrylic resin prepolymer A1 and the long-chain polyol. (Mole ratio [OH _A / OH _P ]) was 1.0.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 41 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface layer forming liquid (polymer B1).

<Formation of laminated body (B1)>
As the base material 2, a PVC leather for automobiles (manufactured by Kyowa Leather Co., Ltd.) having a thickness of 0.8 mm was prepared.
The surface layer forming liquid (polymer B1) was applied onto the base material with a wire bar and then cured at 85 ° C. for 1 hour to form a surface layer (B1) having a film thickness of 30 μm on the base material. In this way, a laminated body (B1) was obtained.

[Example B2]
<Preparation of surface layer forming liquid (polymer B2)>
In the preparation of the first solution, instead of the hydroxyl group-containing double-ended modified silicone resin (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent of 1500 g / mol), the double-ended modified silicone resin having a hydroxyl group (KF-) 6002, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 35 g / mol) except that 1.0 part was added, the surface layer forming liquid (polymer B2) was prepared in the same manner as the above-mentioned preparation of the surface layer forming liquid (polymer B1). ) Was obtained.

<Formation of laminated body (B2)>
A laminated body (B2) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer B2) was used instead of the surface layer forming liquid (polymer B1).

[Example B3]
<Preparation of surface layer forming liquid (polymer B3)>
In the preparation of the first solution, instead of the hydroxyl group-containing double-ended modified silicone resin (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent of 1500 g / mol), the double-ended modified silicone resin having a hydroxyl group (KF-) 6003, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 22 g / mol) except that 0.2 part was added, the surface layer forming liquid (polymer B3) was prepared in the same manner as the above-mentioned preparation of the surface layer forming liquid (polymer B1). ) Was obtained.

<Formation of laminated body (B3)>
A laminated body (B3) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer B3) was used instead of the surface layer forming liquid (polymer B1).

[Example B4]
<Preparation of surface layer forming liquid (polymer B4)>
In the preparation of the first solution, instead of the hydroxyl group-containing double-ended modified silicone resin (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent of 1500 g / mol), the double-ended modified silicone resin having a hydroxyl group (KF-) 6002, manufactured by Shinetsu Chemical Industry Co., Ltd., functional group equivalent 35 g / mol) was added in an amount of 1.5 parts, but the surface layer forming liquid (polymer B4) was prepared in the same manner as in the above preparation of the surface layer forming liquid (polymer B1). ) Was obtained.

<Formation of laminated body (B4)>
A laminated body (B4) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer B4) was used instead of the surface layer forming liquid (polymer B1).

[Reference Example B1]
<Preparation of surface layer forming liquid (polymer BC1)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A1 liquid (solid content 50% by mass): 30 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Corporation, molecular weight 850, hydroxyl value 190-200 mgKOH / g): 29 parts

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 40 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface layer forming liquid (polymer BC1).

<Formation of laminated body (BC1)>
A laminated body (BC1) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer BC1) was used instead of the surface layer forming liquid (polymer B1).

[Reference Example B2]
<Synthesis of acrylic resin prepolymer A6>
Similar to the acrylic resin prepolymer A1, the acrylic resin pre Polymer A6 was synthesized.
Moreover, when the hydroxyl value of the obtained acrylic resin prepolymer A6 was measured according to the method (potentiometric titration method) defined in JIS K0070-1992, the hydroxyl value was 206 mgKOH / g.

<Preparation of surface layer forming liquid (polymer BC2)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A6 liquid (solid content 50% by mass): 64 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Co., Ltd., molecular weight 850, hydroxyl value 190-200 mgKOH / g): 28 parts -Both end-modified silicone resin having hydroxyl groups (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 0.2 parts The amount of total hydroxyl groups of the acrylic resin prepolymer BA11 and the long-chain polyol. (Mole ratio [OH _A / OH _P ]) was 1.0.

In addition, the following second solution was prepared.
Second solution (polyfunctional isocyanate, duranate TPA100, manufactured by Asahi Kasei Chemicals, compound name: polyisocyanurate of hexamethylene diisocyanate): 34 parts

The second solution was added to the first solution and defoamed under reduced pressure for 10 minutes. Further, a reaction catalyst (inorganic bismuth) was added to prepare a surface layer forming liquid (polymer BC2).

<Formation of laminated film (BC2)>
A laminated body (BC2) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer BC2) was used instead of the surface layer forming liquid (polymer B1).

[Reference Example B3]
<Preparation of surface layer forming liquid (polymer BC3)>
In the preparation of the first solution, instead of the double-ended modified silicone resin having a hydroxyl group (KF-9701, manufactured by Shinetsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol), the one-ended modified silicone resin having a hydroxyl group (X-) 22-170DX, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 12 g / mol), except that 1 part was added, the surface layer forming solution (polymer BC3) was prepared in the same manner as the above surface layer forming solution (polymer B1). ) Was obtained.

<Formation of laminated film (BC3)>
A laminated body (B3) was obtained in the same manner as in the formation of the laminated body (B1) except that the surface layer forming liquid (polymer B3) was used instead of the surface layer forming liquid (polymer B1).

[Measurement and evaluation of physical properties]
The physical properties of the laminate having the surface layer obtained in each example were measured and evaluated by the following methods. The results are shown in Table 2.

(Measurement of physical properties)
-Fluorine atomic weight on the surface-
Fluorine atom amount at the outermost surface of the surface protective member [F _S], fluorine atom amount at the surface after etching for 1 minute with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface [F _{I-1 ], And the fluorine atomic weight [FI-20} ] on the surface after etching the outermost surface 2 mm square with an argon gas cluster ion gun having an output of 5 kV for 20 minutes was measured by the above-mentioned method.

-Silicon atomic weight on the surface-
Fluorine atom amount at the outermost surface of the surface protective member [S _S], a silicon atom content at the surface after etching for 1 minute with argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface [S _{I-1 ], And the silicon atomic weight [SI-20} ] on the surface after etching the outermost surface 2 mm square with an argon gas cluster ion gun having an output of 5 kV for 20 minutes was measured by the above-mentioned method.

(Evaluation of shape followability)
The laminated film obtained in each example was cut out to a width of 25 mm and a length of 150 mm. Mark the laminated film at the position of 25 mm on both long ends of the cut out laminated film, sandwich the laminated film with a jig at the marked line position, and use a tensile tester (Strograph V1-C type manufactured by Toyo Seiki Co., Ltd.) at a speed of 50 mm / A tensile test was performed in min until the marked line distance became 110 mm. The surface condition of the coated surface after the test was visually observed and evaluated according to the following evaluation criteria.

-Evaluation criteria A (○): No change B (△): Partially deformed coating film C (×): Surface broken or peeled off

As shown in Table 2, the laminates obtained in each example containing a silicone resin having a plurality of functional groups that are reactive with isocyanate groups have adhesiveness between the supporting base material and the surface resin layer over time. Excellent and excellent in followability.

Claims (14)

Supporting base material made of leather and
A surface resin layer arranged in contact with the supporting substrate, which has a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, has an acrylic resin containing a fluorine atom, has a plurality of hydroxyl groups, and has the hydroxyl groups. A surface resin layer containing a polyacrylic urethane resin which is a cured product of a resin composition containing a polyol via a carbon chain having 6 or more carbon atoms and a polyfunctional isocyanate.
Laminated body having. Fluorine atom amount at the outermost surface of the surface resin layer [F _S] and the fluorine atom amount at the surface after 20 minutes etching with argon gas cluster ion gun 2mm square range output 5kV outermost surface [F The laminate according to claim 1, wherein the ratio of [ _{I-20 ] to [(FI-20} / F _S ) × 100 (%)] is 2% or more and 50% or less. The fluorine atom amount at the outermost surface of the surface resin layer _{[F S]} is laminate according to claim 1 or claim 2 or less 5 atm% or more 22 atm%. The outermost fluorine atom amount at the outer surface _{[F S]} is laminate according to claim 3 or less 15 atm% or more 22 atm%. The laminate according to any one of claims 1 to 4, wherein the content of the fluorine atom in the polyacrylic urethane resin is 1.5% by mass or more and 8.0% by mass or less. The resin composition has a molar ratio [OH _A / OH _P ] of 0.1 or more between the amount of all hydroxyl groups in the acrylic resin [OH _A ] and the amount of all hydroxyl groups in the polyol [OH _P]. 4. The laminate according to any one of claims 1 to 5, which is 4 or less. The laminate according to any one of claims 1 to 6, wherein the surface resin layer has an average thickness of 10 μm or more and 100 μm or less. The laminate according to any one of claims 1 to 7, wherein the leather is at least one selected from the group consisting of polyurethane-based synthetic leather, vinyl chloride-based synthetic leather, and natural leather. The resin composition contains a silicone resin having a plurality of functional groups that are reactive with isocyanate groups.
The fluorine atom amount at the outermost surface of the surface resin layer _{[F S]} is not more than 22 atm%, and the silicon atom content in the outermost surface _{[S S]} is less 2 atm% or more 6 atm%, of the outermost surface the ratio of the fluorine atom amount at the surface after etching for 1 minute with argon gas cluster ion gun output 5kV a range of 2mm square _{[F I-1]} and the _{[F S] [(F I} -1 / F S) _{× 100 (%)] is 0% or more and 70% or less, and the silicon atomic weight [SI-] on} the surface after etching the outermost surface 2 mm square area with an argon gas cluster ion gun having an output of 5 kV for 1 minute. _1] and the _{[S S]} and ratio _{[(S I-1 / S} S) × 100 (%)] is described in any one of claims 1 to 8 or less 70% 20% Laminated body. The laminate according to claim 9, wherein the silicone resin is a silicone resin having two functional groups in one molecular structure. The 9th or 10th claim, wherein the silicone resin has at least one group selected from the group consisting of an amino group, a hydroxyalkyl group, a hydroxyl group, a carboxyl group, a silanol group and an epoxy group as the functional group. The laminate described. The ratio [(FI _-1 / F _S ) × 100 (%)] of the cured product is 10% or more and 50% or less, and the ratio [(SI _-1 / S _S ) × 100 (%)] is The laminate according to any one of claims 9 to 11, which is 30% or more and 60% or less. After the ratio [(FI _-20 / F _S ) × 100 (%)] is 40% or less and the outermost surface 2 mm square is etched with an argon gas cluster ion gun having an output of 5 kV for 20 minutes. the silicon atom content at the surface _{[S I-20]} with the _{[S S]} ratio of _{[(S I-20 / S} S) × 100 (%)] is less than 40% 0% claim 9 wherein Item 2. The laminate according to any one of Item 12. The laminate according to any one of claims 9 to 13, wherein the content of the silicone resin is 0.1% by mass or more and 1% by mass or less with respect to the cured product.