JP2021107489A - Surface protection resin member, and solution set for forming surface protection resin member - Google Patents

Abstract

To provide a surface protection member suppressed in whitening, or to provide a solution set for forming the surface protection member.SOLUTION: A surface protection resin member as a cured product of a resin composition containing predetermined resin is such that: a fluorine atom amount [FS] on an outermost surface is 12 atm% or more and 22 atm% or less; a silicon atom amount [SS] on the outermost surface is 2 atm% or more and 6 atm% or less; a ratio [(FI-1/FS)×100(%)] of a fluorine atom amount [FI-1] on the surface after etching the outermost surface for one minute to the [FS] is 0% or more and 70% or less; and a ratio [(SI-1/SS)×100(%)] of a silicon atom amount [SI-1] on the surface after etching the outermost surface for one minute to the [SS] is 20% or more and 70% or less.SELECTED DRAWING: None

Description

The present invention relates to a surface protective resin member and a solution set for forming the surface protective resin member.

Conventionally, in various fields, processing has been performed on the surface of a steel sheet or a decorative sheet to which a design property has been imparted for the purpose of providing a surface protection resin portion layer for the purpose of surface protection. 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 describes a decorative sheet obtained by laminating at least a decorative layer, a primer layer, and a surface protective layer on a base material made of a polyolefin resin, wherein the surface protective layer is (1) carbon. Urethane acrylate (A) having 13 to 25 long-chain alkyl groups and ionizing thermosetting functional groups and modified with polycaprolactone, organic isocyanate having two or more isocyanate groups in one molecule, and hydroxy The urethane acrylate (B) obtained by reacting the modified (meth) acrylate and the polycaprolactone-containing polyfunctional alcohol has a compounding mass ratio of the urethane acrylate (A) and the urethane acrylate (B) of 25:75 to 75:25. It is obtained by cross-linking and curing the ionizing thermosetting resin blended in (2) with a coating thickness of 10 to 50 μm, and (3) the coating with the ionizing thermosetting resin of (1) having a thickness of 140 μm. After coating and curing the ionizing thermosetting resin to a thickness of 15 μm on the polypropylene film, a tensile test is performed at a temperature of 25 ° C. and a tensile speed of 50 mm / min to measure the elongation at break. Decorative sheets are disclosed in which the measured tensile elongation is 50-90%.

Further, Patent Document 2 describes a self-repairing protective sheet in which a self-repairing layer is laminated on one side of a thermoplastic elastomer base material, and the self-repairing layer is at least urethane resin (A), silicone resin (B), and isocyanate ( C) is thermally crosslinked, and the thermoplastic elastomer base material has a maltens hardness of 0.1 to 10.0 N / mm ² and the self-healing layer has a maltens hardness of 50 to 300 mN / mm ^2. The self-healing protective sheet is disclosed.

Further, Patent Document 3 is a decorative sheet having at least a base sheet, a resin layer arranged on the base sheet, and a surface coat layer covering the outer surface of the resin layer, and the surface coat. A decorative sheet is disclosed, wherein the layer is formed of a resin component containing a fluorine-based component and / or a silicone-based component.

Further, Patent Document 4 describes a laminated film having an A layer on at least one side of the base film, the A layer having (1) (poly) caprolactone segment and (2) urethane bond. The contact angle of the distilled water on the A layer is 95 ° or more and less than 120 °, the contact angle of diiodomethane on the A layer is 70 ° or more and less than 87 °, and the A layer is the following fluorine compound A ( Fluorocompound A represents a reactive moiety or hydroxyl group, R1 represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived from them, Rf represents a fluoroalkyl group, each having a side chain in the structure. A component derived from (may be)) (hereinafter, referred to as a fluorine compound A-derived component) is contained, and the fluorine compound A-derived component is 0.5% by mass or more and 25% by mass or less in 100% by mass of all the components of the layer A. Laminated films comprising include are disclosed.

Japanese Unexamined Patent Publication No. 2013-078847 JP-A-2017-177742 Japanese Unexamined Patent Publication No. 2007-32112 International Publication No. 2012/157500

The member provided on the surface of the article for the purpose of surface protection includes an acrylic resin and a surface protection resin member having a polyol or caprolactone segment via a carbon chain having 6 or more carbon atoms (hereinafter, also simply referred to as “surface protection member”. ) Is sometimes used, but when pressure or tension is locally applied to the above-mentioned surface protection member having a resin, a phenomenon called stress whitening occurs, and the surface protection member may be whitened.

The subject of the present invention is
The surface protection member
(I) A polyfunctional resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less and containing a fluorine atom, and a polyol having a plurality of hydroxyl groups and having the hydroxyl group via a carbon chain having 6 or more carbon atoms. When it is a cured product of a resin composition composed of isocyanate and
(Ii) 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 a hydroxyl group having 6 or more carbon atoms via a carbon chain, and an isocyanate. When it is a cured product of a resin composition composed of a silicone resin having a plurality of functional groups exhibiting reactivity with a group and a polyfunctional isocyanate, or
(Iii) An acrylic resin having a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, containing a fluorine atom, a polyol having a plurality of hydroxyl groups and having a hydroxyl group having 6 or more carbon atoms via a carbon chain, and an isocyanate group. Compared with the case of a cured product of a resin composition composed of a silicone resin having only one functional group exhibiting reactivity with respect to a polyfunctional isocyanate and a polyfunctional isocyanate.
It is to provide a surface protection member in which whitening is suppressed, or a solution set for forming the surface protection member.

The above problem is solved by the following means.
<1>
With respect to 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, and an isocyanate group. a silicone resin having a plurality of functional groups reactive, a cured product of the resin composition containing a polyfunctional isocyanate, a fluorine atom amount at the outermost surface [F _S] is more than 12 atm% 22 atm% or less, and the silicon atom amount at the outermost surface [S _S] is less 2 atm% or more 6 atm%, said 2mm square range output 5kV outermost surface of an argon gas cluster ion gun for 1 minute etched surface after fluorine amount _{[F I-1]} and the _{[F S]} and the ratio in _{[(F I-1 / F} S) × 100 (%)] is less than 70% 0% and 2mm square of the outermost surface _{Ratio of silicon atomic weight [SI-1} ] on _{the surface to the above [SS} ] [(SI _-1 / _SS ) × 100 after etching the range of 5 kV with an argon gas cluster ion gun for 1 minute. (%)] Is 20% or more and 70% or less.
<2>
The surface protective resin member according to <1>, wherein the silicone resin is a silicone resin having two functional groups in one molecular structure.
<3>
The silicone resin has <1> or <2> 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 surface protective resin member described.
<4>
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 surface protective resin member according to any one of <1> to <3>, which is 30% or more and 60% or less.
<5>
The ratio of the the highest fluorine atom amount at 2mm square surface after 20 minutes etching with argon gas cluster ion gun output 5kV range of the outer surface _{[F I-20] [F} S] [(F I- _{20 / F S) × 100 (} %)] is not more than 40% 0% and the silicon on the outermost surface 2mm square surface after 20 minutes etching with argon gas cluster ion gun output 5kV a range of any atomic weight _{[S I-20]} with the _{[S S]} ratio of _{[(S I-20 / S} S) × 100 (%)] is less than 40% 0% <1> to the <4> The surface protection resin member according to one.
<6>
The molar ratio [OH _A / OH _P ] of the amount of total hydroxyl groups [OH _A ] in the acrylic resin and the amount of total hydroxyl groups [OH _P ] in the polyol is 0.1 or more and 4 or less <1. > The surface protective resin member according to any one of <5>.
<7>
The surface protective resin member according to any one of <1> to <6>, 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.
<8>
Described in any one of <1> to <7>, wherein the Martens hardness at 23 ° C. is 0.5 N / mm ² or more and 220 N / mm ² or less, and the return rate at 23 ° C. is 70% or more and 100% or less. Surface protection resin member.
<9>
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. A first solution containing a silicone resin having a plurality of reactive functional groups, a second solution containing a polyfunctional isocyanate, and the like.
A solution set for a surface protective resin member formed containing, the first fluorine atom amount at the outermost surface of the cured product of the mixture of solution and the second solution [F _S] is less 12 atm% or more 22 atm% in, and a silicon atom content in the outermost surface [S _S] is less 2 atm% or more 6 atm%, after the for 1 minute etch in argon gas cluster ion gun output 5kV a 2mm square range of the outermost surface fluorine atom amount at the surface _{[F I-1]} and the _{[F S]} and ratio _{[(F I-1 / F} S) × 100 (%)] is 70% or less than 0%, and the outermost surface After etching a 2 mm square area with an argon gas cluster ion gun with an output of 5 kV for 1 minute _{, the ratio of the silicon atomic weight [SI-1} ] on _{the surface to the above [SS} ] [(SI _-1 / _SS) ) X 100 (%)] is 20% or more and 70% or less, a solution set for forming a surface protective resin member.

According to the invention according to <1> or <8>
The surface protection member
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.
A surface protective resin member that suppresses whitening is provided.
According to the invention according to <2>
Provided is a surface protective resin member in which whitening is suppressed 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 <3>
Provided is a surface protection resin member in which whitening is suppressed as compared with the case where the silicone resin has an alkyl group or an aryl group, an alkylaryl group, or an arylalkyl group as the functional group.
According to the invention according to <4>
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 provided as a surface protective resin member in which whitening is suppressed as compared with the case where it is less than 30% or more than 60%.
According to the invention according to <5>
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 surface protecting resin member whitening is suppressed Provided.
According to the invention according to <6>
Compared to the case where the molar ratio [OH _A / OH _P ] of the amount of total hydroxyl groups [OH _A ] in the acrylic resin and the amount of total hydroxyl groups [OH _P ] in the polyol is less than 0.1 or more than 4. Therefore, a surface protective resin member that suppresses whitening is provided.
According to the invention according to <7>
Provided is a surface protective resin member in which whitening is suppressed 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.
According to the invention according to <9>
The first liquid for forming the surface protective resin member is
When the hydroxyl group value is 40 mgKOH / g or more and 280 mgKOH / g or less, and is composed of an acrylic resin containing a fluorine atom and a polyol having a plurality of hydroxyl groups and having the hydroxyl group via a carbon chain having 6 or more carbon atoms.
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. When composed of a silicone resin having a plurality of functional groups exhibiting reactivity, or
With respect to 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, and an isocyanate group. Compared to the case consisting of a silicone resin having only one reactive functional group,
Provided is a solution set for forming a surface protective resin member in which whitening of the surface protective member is suppressed.

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.

<Surface protection resin member>
The surface protection resin member (surface protection member) according to the present embodiment has a hydroxyl value of 40 mgKOH / g or more and 280 mgKOH / g or less, and includes a plurality of acrylic resins (hereinafter, also referred to as “specific acrylic resin”) containing a fluorine atom. The hydroxyl group has a polyol having a carbon chain having 6 or more carbon atoms (hereinafter, also referred to as “long-chain polyol”), and a plurality of functional groups exhibiting reactivity with an isocyanate group. It is a cured product of a resin composition containing a silicone resin (hereinafter, also referred to as “isocyanate-based reactive silicone resin”) and polyfunctional isocyanate.
The surface protecting member is a fluorine atom amount at the outermost surface _{[F S]} is not more than 12 atm% or more 22 atm%, and the silicon atom content in the outermost surface _{[S S]} is less 2 atm% or more 6 atm%, the ratio of the fluorine atom amount at the outermost surface 2mm square surface after etching for 1 minute with argon gas cluster ion gun output 5kV a range of _{[F I-1] [F} S] [(F I- _{1 / F S) × 100 (} %)] is not more than 70% 0% and the silicon on the outermost surface 2mm square surface after etching for 1 minute range with argon gas cluster ion gun output 5kV of atomic weight _{[S I-1]} and the ratio _{[(S I-1 / S} S) × 100 (%)] and _{[S S]} is 70% or less than 20%.

As the surface protection member according to the present embodiment, by satisfying the above configuration, a surface protection member in which whitening is suppressed can be obtained.
The reason can be inferred as follows.

First, as a surface protection resin member (surface protection member), a cured product of a resin composition composed of a specific acrylic resin, a long-chain polyol, and a polyfunctional isocyanate tends to be excellent in self-healing property and abrasion resistance. There is. In particular, the surface protective resin member (the surface protective member), a fluorine atom amount at the outermost surface [F _S] is is not more than 12 atm% or more 22 atm%, the resin surface energy moderately reduced in the outermost surface, good It is considered to show antifouling property.
_{Focusing on the gradient of the fluorine atomic weight in the surface protection member, the fluorine atomic weight [FI-1} ] 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 1 minute. wherein the ratio of the _{[F S] [(F I} -1 / F S) × 100 (%)] is less than 70% 0%, fluorine atoms are present in high density in the outermost surface of the resin It can be seen that the density is low in the inner layer. When a solution set for forming a surface protective resin member capable of forming such a gradient is used and applied to an article (also referred to as a "base material"), the influence of fluorine atoms present at the interface of the article is reduced. Therefore, it is considered that a product having excellent adhesion to the base material can be obtained.
However, as described above, when pressure or tension is locally concentrated on such a surface protection member, a phenomenon called stress whitening occurs, and the surface protection member may be whitened.

Surface protection member according to the present embodiment includes an isocyanate group-reactive silicone resin, a silicon atom amount at the outermost surface of the surface protective member [S _S] is less 2 atm% or more 6 atm%, also, the outermost the ratio of the silicon atoms of the surface after etching 1 minute 2mm square range with argon gas cluster ion gun output 5kV surface _{[S I-1]} and the with _{[S S] [(S I} -1 / S _S ) × 100 (%)] is 20% or more and 70% or less.
In the surface protection member according to the present embodiment, the silicon atom of the silicone resin is localized on the outermost surface as well as the fluorine atom, but is also present inside. Since the component containing a fluorine atom and the component containing a silicon atom are difficult to be compatible with each other, the component containing a silicon atom is considered to assist the localization of the fluorine atom on the surface. .. It is considered that the presence of the silicon atom on the outermost surface relaxes the interaction between the carbon chains of the acrylic resin and the polyol, which causes stress whitening, so that whitening can be prevented.
That is, since the surface protection member according to the present embodiment uses an acrylic resin containing fluorine atoms, it is predicted that whitening is likely to occur due to the interaction between fluorine atoms having low polarity, and therefore the silicone resin is further contained. Therefore, it is considered that the silicon atoms contained in the silicone resin are present so as to assist the localization of the fluorine atoms on the surface, and the silicon atoms relax the interaction between the fluorine atoms. In other words, the relaxation of the interaction between fluorine atoms indicates that slipperiness is imparted to the molecules in the surface protection member, and thus it is considered that whitening of the surface protection member is prevented.

(Fluorine atomic weight)
In the present embodiment, the surface protective member, the fluorine atom amount at the outermost surface _{[F S]} is less than 12 atm% or more 22 atm%. Also, the 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 ratio of [F _S] [(F _{I -1 / F S) × 100 (} %)] is less than 70% 0%.

The fluorine atom amount at the outermost surface [F _S] is less than 12 atm%, the water and oil repellency is insufficient, antifouling property may well not obtained trend. Also, the fluorine atom amount at the outermost surface [F _S] is at more than 22 atm%, the amount of fluorine atoms is excessive, adhesion to the substrate tends to be low.
Fluorine atom amount at the outermost surface _{[F S]} is preferably less than 15atm% 21atm%.

Further, when the above ratio [(FI _-1 / F _S ) × 100 (%)] exceeds 70%, high adhesion to the base material tends not to be obtained.
Further, from the viewpoint of obtaining a surface protection member in which whitening is suppressed, the above ratio [(FI _-1 / F _S ) × 100 (%)] is preferably 10% or more and 50% or less, and more preferably 10. % Or more and 40% or less.

In the present embodiment, from the viewpoint of obtaining a surface protective member whitening is suppressed, the surface protective member, the fluorine atom amount at the outermost surface and the [F _S], argon gas output 5kV a 2mm square range of the outermost surface fluorine atom amount at the surface and _{[F I-20],} the ratio of _{[(F I-20 / F} S) × 100 (%)] is less than 40% 0% after etching for 20 minutes at cluster ion gun It is more preferable, it is more preferably 0% or more and 30% or less, further preferably 0% or more and 20% or less, and further preferably 0% or more and 15% or less.

(Silicon atomic weight)
In the present embodiment, the surface protective member, the silicon atom content in the outermost surface _{[S S]} is less than 2 atm% or more 6 atm%. Also, the 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 ratio of the [S _S] [(S _{I -1 / S S) × 100 (} %)] is 70% or less than 20%.

If the silicon atom content in the outermost surface [S _S] is less than 2 atm%, it becomes difficult to alleviate the interaction between the fluorine atom at the outermost surface, whitening inhibition tends to decrease. Further, when the silicon atom content in the outermost surface [S _S] is at more than 6 atm%, it tends to inhibit localized in the outermost surface of the fluorine atoms in the outermost surface, reduces the water and oil repellency, Antifouling properties tend to decrease.
Silicon atom amount at the outermost surface _{[S S]} is preferably less than 3 atm% 6 atm%.

Further, when the ratio _{[(S I-1 / S} S) × 100 (%)] is 70 percent, since the amount of the silicone resin is excessive, the water and oil repellency tends to decrease, stain resistance Is not sufficiently obtained, and further, when the substrate is coated, a large amount of silicon atoms are present at the interface and the adhesion tends to be lowered. Further, when the ratio _{[(S I-1 / S} S) × 100 (%)] is less than 20%, there tends to be no longer exhibit sufficient anti-whitening effect.
From the viewpoint of obtaining a surface protective member in which whitening is suppressed, the above ratio [(SI _-1 / _SS ) × 100 (%)] is preferably 30% or more and 60% or less, and more preferably 30% or more. It is 50% or less.

In the present embodiment, from the viewpoint of obtaining a surface protective member whitening is suppressed, the surface protective member, the silicon atom content in the outermost surface and the [S _S], argon gas output 5kV a 2mm square range of the outermost surface The ratio [(SI _-20 / _{SS ) x 100 (%)] to the silicon atomic weight [SS-20} ] on the surface after etching with a cluster ion gun for 20 minutes is 0% or more and 40% or less. It is more preferable, it is more preferably 0% or more and 30% or less, further preferably 0% or more and 20% or less, and further preferably 0% or more and 15% or less.

Here, a method for measuring the atomic weight of fluorine and the atomic weight of silicon will be described.
Fluorine atomic weight and silicon atomic weight are 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 protection member will be described.
Specifically, an area of 2 mm square on the outermost surface of the surface protection member 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)

Further, from the viewpoint of obtaining a surface protective member which whitening is suppressed, the surface protective member, the fluorine atom amount at the outermost surface and the [F _S], fluorine atom amount at the interface between the substrate and the [F _B], the ratio of _{[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 with the substrate of the surface protective member for the measuring method of [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 laminated member having a base material and a surface protection member. 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.

Fluorine atom amounts of proportions and methods of accomplishing the ratio of silicon atoms amount then the ratio _{[(F I-1 / F} S) × 100 (%)], the ratio _{[(S I-1 / S} S) × 100 (%)] , the ratio _{[(F I-20 / F} S) × 100 (%)], and the ratio _{[(S I-20 / S} S) × 100 (%)] to be described a method of controlling the above range. The ratio _{[F B / F S × 100} (%)] can also be controlled by the following method.
The achievement method is not particularly limited, and examples thereof include the following methods.

Achievement method (1)
The resin constituting the surface protection member is a polymer of a specific acrylic resin (a) having a fluorine atom, a long-chain polyol (b), an isocyanate group-reactive silicone resin (c), and a polyfunctional isocyanate (d).
Since the fluorine atom has low compatibility with the long-chain polyol (b) and the polyfunctional isocyanate (d), the specific acrylic resin (a) having a fluorine atom is likely to be oriented toward the outermost surface side of the surface layer. On the other hand, the long-chain polyol (b) and the polyfunctional isocyanate (d) are likely to be oriented toward the interface with the base material. Further, the silicone resin having a silicon atom has low compatibility with the long-chain polyol (b) and the polyfunctional isocyanate (d) like the fluorine atom, and also has low compatibility with the specific acrylic resin having a fluorine atom. Since the silicone resin having a plurality of isocyanate group-reactive groups does not bond with the acrylic skeleton and further reacts with only the polyfunctional isocyanate with a plurality of reactive groups, it is easy to orient the outermost surface and the inside.
It is considered that this makes it easier to control the ratio of the fluorine atomic weight and the silicon atomic weight ratio within the above range.

Achievement method (2)
Further, from the viewpoint of controlling the ratio of the fluorine atomic weight and the silicon atomic weight ratio within the above range, the SP value (solubility parameter) of the resin contained in the base material is preferably 8.1 or more. When the SP value of the resin in the base material is 8.1 or more, the reason why the ratio of the fluorine atomic weight and the ratio of the silicon atomic weight can be easily controlled within 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 (d) toward the interface with the substrate, while the specific acrylic resin (a) having a fluorine atom and the isocyanate group-reactive silicone. It is considered that the resin (c) is easily oriented toward the outermost surface side of the surface layer.
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 resin, and the adhesion between the surface protection member 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 (d) in the surface protection member 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) containing a fluorine atom, 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 protection member, that is, the side chain portion having the fluorine atoms is exposed on the outermost surface of the surface protection member. It is considered to have mobility. Therefore, the specific acrylic resin (a) having a fluorine atom is easily oriented toward the outermost surface side of the surface protection member, while the long-chain polyol (b) and the polyfunctional isocyanate (d) are oriented toward the interface side with the base material. It is thought that it will be easier to make. Further, in the isocyanate group-reactive silicone resin (c), since only the isocyanate reaction portion reacts with the polyfunctional isocyanate, the silicone structure portion can move freely, and the long-chain polyol (b) and the polyfunctional isocyanate ( It does not prevent d) from being oriented toward the interface with the substrate.

Next, each component of the resin composition forming the surface protective resin member according to the present embodiment will be described in detail.

The surface protective resin member according to the present embodiment is obtained by polymerizing a resin composition containing a specific acrylic resin (a), a long-chain polyol (b), an isocyanate group-reactive silicone resin (c), and a polyfunctional isocyanate (d). It is a cured product.

(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 preferably has a fluorine atom in its molecular structure. By containing fluorine atoms in the specific acrylic resin, the antifouling property is enhanced, and it becomes easy to form a surface protective resin member having a low surface friction coefficient.
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 200 mgKOH / g or less.
When the hydroxyl value is 40 mgKOH / g or more, a polyurethane resin having a high crosslink density is polymerized, while when it is 280 mgKOH / g or less, a polyurethane resin having appropriate flexibility can be obtained.
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 protection member 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) 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 (c) via the polyfunctional isocyanate (d), a siloxane bond is introduced into the side chain of the specific acrylic resin (a) and formed. The coefficient of friction of the surface protective resin member 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, it is preferable to have 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, and preferably having a hydroxyalkyl group or a hydroxyl group. Is more preferable.
The isocyanate group-reactive silicone resin has 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 ease of movement of the chain having a siloxane bond is further improved, the portion having a silicon atom is easily exposed on the surface of the surface protective resin member, and the friction coefficient of the surface protective resin member is more likely to be reduced.
When two of the functional groups are contained in one molecular structure, the position of the functional groups is 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 protective resin member. More preferably.

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 each independently reactive with an isocyanate group, and R ³¹ is reactive with a hydrogen atom, an alkyl group, an aryl group, or an isocyanate group. The functional group shown, 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 a structure represented by the general formula (P1) has a structure in which the functional groups are contained only in ^{X 11} and X ^12.

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.

(D) Polyfunctional isocyanate The polyfunctional isocyanate (d) is a compound having a plurality of isocyanate groups (-NCO), for example, a hydroxyl group of the specific acrylic resin (a), a hydroxyl group of the long-chain polyol (b), and silicone. It reacts with a functional group or the like that is reactive with the isocyanate group of the resin (c). Then, it functions as a cross-linking agent for cross-linking the specific acrylic resins (a) with each other, the specific acrylic resin (a) with the long-chain polyol (b), the long-chain polyol (b), and the like.

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.

(E) Other Additives The resin composition forming the surface protective member 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 (d) 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 this embodiment, the surface resistance of the surface protection member to be formed ^{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 ×. It is preferable to adjust the range so that it is in the range of 10 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 protection member 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 (d), 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.

<Solution set for forming surface protective resin member>
The solution set for forming the surface protective resin member of the present embodiment 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 the hydroxyl group has a carbon number of carbons. A surface containing a first solution containing a polyol having 6 or more carbon chains and a silicone resin having a plurality of functional groups reactive with isocyanate groups, and a second solution containing polyfunctional isocyanate. A solution set for forming a protective resin member.
Further, the mixture of the first solution and the second solution, the cured fluorine atom amount at the outermost surface of the cured product formed by [F _S] is more than 12 atm% 22 atm% or less, and the outermost surface the silicon atom content in the [S _S] is less 2 atm% or more 6 atm%, the fluorine atom amount at the surface after etching 1 minute 2mm square range with argon gas cluster ion gun output 5kV of the outermost surface [F _I-1] and the _{[F S]} ratio of _{[(F I-1 / F} S) × 100 (%)] is not more than 70% 0% and outputs a 2mm square range of the outermost surface the silicon atom content at the surface after etching for 1 minute with argon gas cluster ion gun 5kV _{[S I-1]} and the ratio of the _{[S S] [(S I} -1 / S S) × 100 (%)] Is 20% or more and 70% or less.

-Formation of surface protection resin member-
The surface protective resin member according to the present embodiment includes the first solution containing the above-mentioned specific acrylic resin (a), long-chain polyol (b), and isocyanate group-reactive silicone resin (c), and the above-mentioned polyfunctional isocyanate (d). ) Is mixed and cured to form the resin.

Further, the specific acrylic resin (a) and the long-chain polyol are not limited to the case where the first solution (hereinafter, also referred to as “Liquid A”) and the second solution (hereinafter, also referred to as “Liquid B”) are used. It can be formed by reacting (b), an isocyanate group-reactive silicone resin (c), and a polyfunctional isocyanate (d) and curing the mixture.

Here, a method for forming the surface protective resin member (resin polymerization method) according to the present embodiment will be described with reference to a specific example.
For example, a solution A containing a specific acrylic resin (a), a long-chain polyol (b), and an isocyanate group-reactive silicone resin (c), and a solution B containing a polyfunctional isocyanate (d) are prepared. .. The liquids A and B are mixed, defoamed under reduced pressure, and then cast onto a base material (for example, a polyimide film, an aluminum plate, a glass plate, etc.) to form a resin layer. It can then be formed by heating (eg, 85 ° C. for 60 minutes, then 160 ° C. for 0.5 hours) to cure.
However, in the present embodiment, the method for forming the surface protective resin member is not limited to the above method. For example, when a blocked polyfunctional isocyanate is used, it is preferable to heat it to a temperature higher than the temperature at which the block is removed to cure it. Further, the polymerization may be carried out by using ultrasonic waves instead of defoaming under reduced pressure, or by leaving the mixed solution to defoam.

The isocyanate group-reactive silicone resin (c) contained in the first solution (solution A) contains functional groups that are reactive with isocyanate groups in one molecular structure from the viewpoint of low friction coefficient of the surface protective resin member. It is preferable that the silicone resin has two of them.

The content of the silicone resin with respect to the total solid content of the cured product of the resin composition in the surface protection resin member according to the present embodiment is 0.1% by mass or more and 10% by mass from the viewpoint of suppressing whitening of the surface protection member. It is preferably 0.1% by mass or more and 1% by mass or less.

The thickness of the surface protection resin member is not particularly limited, but may be, for example, 1 μm or more and 100 μm or less, and may be 10 μm or more and 30 μm or less.

-Martens hardness The surface protective resin member according to the present embodiment preferably has a Martens hardness at 23 ° C. of 0.5 N / mm ² or more and 220 N / mm ² or less, and 1 N / mm ² or more and 80 N / mm ² or less. more preferably in, still more preferably 1N / mm ² or more 70N / mm ² or less, and more preferably 1N / mm ² or more 5N / mm ² or less. When the Martens hardness (23 ° C.) is 0.5 N / mm ² or more, it becomes easy to maintain the shape required for the resin member. On the other hand, when it is 220 N / mm ² or less, the ease of repairing scratches (that is, self-healing property) is likely to be improved.

-Return rate The surface protective resin member according to the present embodiment preferably has a return rate of 70% or more and 100% or less at 23 ° C., more preferably 80% or more and 100% or less, and 90% or more and 100%. It is more preferably less than or equal to%. The return rate is an index showing the self-healing property of the resin material (the property of restoring the strain formed by stress within 1 minute after the stress is unloaded, that is, the degree of scratch repair). That is, when the return rate (23 ° C.) is 70% or more, the ease of repairing the wound (that is, self-repairing property) is improved.

The Martens hardness and return rate of the surface protective resin member are, for example, the hydroxyl value of the specific acrylic resin (a), the number of carbon atoms of the chain connecting the hydroxyl groups in the long chain polyol (b), and the length with respect to the specific acrylic resin (a). It is adjusted by controlling the ratio of the chain polyol (b), the number of functional groups (isocyanate groups) in the polyfunctional isocyanate (d), the ratio of the polyfunctional isocyanate (d) to the specific acrylic resin (a), and the like.

For the measurement of Martens hardness and return rate, a Fisherscope HM2000 (manufactured by Fisher) is used as a measuring device, and a surface protective resin member (sample) is fixed to a slide glass with an adhesive and set in the measuring device. A load is applied to the surface protective resin member at a specific measurement temperature (for example, 23 ° C.) up to 0.5 mN for 15 seconds, and the surface protective resin member is held at 0.5 mN for 5 seconds. The maximum displacement at that time is (h1). After that, the load is unloaded to 0.005 mN over 15 seconds, and the displacement when held at 0.005 mN for 1 minute is defined as (h2), and the return rate [(h1-h2) / h1] × 100 (%) is calculated. calculate. Further, the Martens hardness can be obtained from the load displacement curve at this time.

[Use]
The surface protective resin member according to the present embodiment can be used as a surface protective member for, for example, an article whose surface may be scratched due to contact with a foreign substance.
Specifically, screens and bodies other than screens in portable devices (for example, mobile phones, portable game machines, etc.), touch panel screens, building materials (for example, floor materials, tiles, wall materials, wallpaper, etc.), automobile parts (for example, cars). Interiors, car bodies, door handles, etc.), storage containers (eg suitcases, etc.), cosmetic containers, glasses (eg frames, lenses, etc.), sporting goods (eg golf clubs, rackets, etc.), writing utensils (eg, golf clubs, rackets, etc.) Permanent brushes, etc.), musical instruments (eg, piano exteriors, etc.), clothing storage tools (eg, hangers, etc.), copiers and other image forming equipment members (eg, transfer belts and other transfer members), leather products (eg, bags, land cells, etc.) Etc.), decorative films, film mirrors, etc.

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.
Moreover, 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.

<Preparation of surface protection member 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): 40 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-Double-ended modified silicone resin having a hydroxyl group (KF-9701, manufactured by Shinetsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 0.5 parts In addition, acrylic resin prepolymer A1 and long-chain polyol. The ratio of the amount of total hydroxyl groups (molar 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 1).

<Formation of laminated film (1)>
An ABS test piece (manufactured by TP Giken Co., Ltd., (trade name) test piece ABS (black)) was prepared as the base material 1.
The surface protection member forming liquid (polymer 1) was applied onto a base material with a wire bar and then cured at 85 ° C. for 1 hour to form a surface protection member (1) having a film thickness of 35 μm on the base material. .. In this way, the laminated film (1) was obtained.

[Example 2]
<Preparation of surface protection member forming liquid (polymer 2)>
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) was added in one part, but the surface protection member forming solution (polymer 2) was prepared in the same manner as in the above preparation of the surface protecting member forming solution (polymer 1). ) Was obtained.

<Formation of laminated film (2)>
A laminated film (2) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 2) was used instead of the surface protective member forming liquid (polymer 1).

[Example 3]
<Preparation of surface protection member forming liquid (polymer 3)>
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 protection member forming liquid (polymer 1) was prepared in the same manner as the above-mentioned surface protection member forming liquid (polymer 1). Polymer 3) was obtained.

<Formation of laminated film (3)>
A laminated film (3) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 3) was used instead of the surface protective member forming liquid (polymer 1).

[Example 4]
<Preparation of surface protection member forming liquid (polymer 4)>
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) was added in an amount of 1.5 parts, but the surface protection member forming solution (polymer 1) was prepared in the same manner as the surface protection member forming solution (polymer 1). Polymer 4) was obtained.

<Formation of laminated film (4)>
A laminated film (4) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 4) was used instead of the surface protective member forming liquid (polymer 1).

[Example 5]
<Synthesis of acrylic resin prepolymer A2>
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 A2 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 A2 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-Double-ended modified silicone resin having a hydroxyl group (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 1.2 parts In addition, acrylic resin prepolymer A2 and long-chain polyol The ratio of the amount of total hydroxyl groups (molar 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 A3>
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 A3 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 A3 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 A3 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-Double-ended modified silicone resin having a hydroxyl group (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 1.0 part In addition, acrylic resin prepolymer A3 and long-chain polyol The ratio of the amount of total hydroxyl groups (molar 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 (5)>
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).

[Comparative Example 1]
<Preparation of surface protection member forming liquid (polymer C1)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A1 liquid (solid content 50% by mass): 40 parts-Long chain polyol (polycaprolactone triol, Praxel 308, manufactured by Daicel Corporation, molecular weight 850, hydroxyl value 190-200 mgKOH / g): 38 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 protection member forming liquid (polymer C1).

<Formation of laminated film (C1)>
A laminated film (C1) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer C1) was used instead of the surface protective member forming liquid (polymer 1).

[Comparative Example 2]
<Synthesis of acrylic resin prepolymer A11>
Acrylic resin prepolymer A11 in the same manner as acrylic resin prepolymer A1 except that the acrylic monomer containing a fluorine atom (having a perfluorohexyl group; FAMAC6, manufactured by Unimatec Co., Ltd.) was replaced with n-butyl methacrylate (nBMA). Was synthesized.
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 206 mgKOH / g.

<Preparation of surface protection member forming liquid (polymer C2)>
After mixing and stirring the following components, a first solution was prepared.
-Acrylic resin prepolymer A11 liquid (solid content 40% 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-Double-ended modified silicone resin having a hydroxyl group (KF-9701, manufactured by Shin-Etsu Chemical Industry Co., Ltd., functional group equivalent 1500 g / mol): 0.5 parts In addition, acrylic resin prepolymer A11 and long-chain polyol The ratio of the amount of total hydroxyl groups (molar 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 C2).

<Formation of laminated film (C2)>
A laminated film (C2) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer C2) was used instead of the surface protective member forming liquid (polymer 1).

[Comparative Example 3]
<Preparation of surface protection member forming liquid (polymer C3)>
In the preparation of the first solution, instead of the double-ended silicone resin having a hydroxyl group (KF-9701, manufactured by Shin-Etsu Chemical Co., Ltd., functional group equivalent 1500 g / mol),
The above-mentioned surface protection member forming liquid (polymer 1) except that one part of a one-terminal modified silicone resin having a hydroxyl group (X-22-170DX, manufactured by Shinetsu Chemical Industry Co., Ltd., functional group equivalent 12 g / mol) was added. A surface protection member forming liquid (polymer C3) was obtained in the same manner as the preparation.

<Formation of laminated film (C3)>
A laminated film (3) was obtained in the same manner as in the formation of the laminated film (1) except that the surface protective member forming liquid (polymer 3) was used instead of the surface protective member forming liquid (polymer 1).

[Measurement and evaluation of physical properties]
The physical properties of the laminated film having the surface protective member obtained in each example were measured and evaluated by the following methods. The results are shown in Table 1.

(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.

Return rate and Martens hardness at -23 ° C-
A Fisherscope HM2000 (manufactured by Fisher) was used as a measuring device, and the obtained laminated film was fixed to a slide glass with an adhesive and set in the above measuring device. The laminated film was loaded at room temperature (23 ° C.) up to 0.5 mN for 15 seconds and held at 0.5 mN for 5 seconds. The maximum displacement at that time is (h1). After that, the load was unloaded to 0.005 mN over 15 seconds, and the displacement when held at 0.005 mN for 1 minute was (h2), and the return rate was "[(h1-h2) / h1] x 100 (%). Was calculated. In addition, the Martens hardness was obtained from the load displacement curve at this time.

(evaluation)
-Evaluation of whitening property-
The surface of the surface protection member obtained in each example was scratched with a load of 21 N using a jig with a ball tip having a tip of 7 mm, and the whitening state of the scratched portion was visually confirmed. It was evaluated according to the evaluation criteria of.
-Evaluation criteria A (○): No whitening B (△): Partial whitening C (×): Significant whitening is seen on the entire surface

-Contact angle with water-
The contact angle with water was measured by the following method.
The contact angle is measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model number: CA-X type).
3 μl of water was dropped on the surface of the surface protection member obtained in each example with a syringe, and measurement was performed. Specifically, the angle formed by the tangent line of the droplet and the surface of the substrate was measured as the contact angle by the θ / 2 method at 25 ° C. Moreover, it was evaluated that the higher the measured value of the contact angle, the higher the antifouling property.

-Evaluation of magic wipeability-
After drawing on the surface protection member obtained in each example with oil-based magic (manufactured by Teranishi Chemical Industry Co., Ltd., large magic ink), after 24 hours, wipe with Bencotton soaked in ethanol for one round trip and evaluate according to the following criteria. did.
-Evaluation criteria A (○): Magic image disappears and no stains remain B (△): Magic image can be slightly confirmed C (×): Magic image remains

-Evaluation of scratch resistance-
While pressing steel wool (# 0000) against the surface of the surface protection resin member obtained in each example under a load of 300 g, the surface characteristics were visually confirmed after rubbing 100 times (that is, 50 reciprocations). Then, it was evaluated according to the following evaluation criteria.
-Evaluation criteria A (○): No scratches confirmed B (△): Several scratches remain slightly C (×): The surface is whitened

-Adhesive crosscut-
For the surface protection member obtained in each example, the adhesion between the base material and the surface protection member was evaluated by the cross-cut method according to JISK5600-5-6 (1999). Evaluation was performed according to the following evaluation criteria.
・ Evaluation criteria A (○): No peeling B (△): Partial peeling C (×): Full peeling

From Table 1, it can be seen that the surface protection member obtained in the examples has suppressed whitening as compared with the one obtained in the comparative example. Further, from Table 2, the surface protective member obtained in the examples shows physical properties that can be seen to be excellent in self-healing property, and is also excellent in antifouling property, magic wiping property, abrasion resistance, and adhesion. It turns out that it is.

Claims (9)

With respect to 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, and an isocyanate group. a silicone resin having a plurality of functional groups reactive, a cured product of the resin composition containing a polyfunctional isocyanate, a fluorine atom amount at the outermost surface [F _S] is more than 12 atm% 22 atm% or less, and the silicon atom amount at the outermost surface [S _S] is less 2 atm% or more 6 atm%, said 2mm square range output 5kV outermost surface of an argon gas cluster ion gun for 1 minute etched surface after fluorine amount _{[F I-1]} and the _{[F S]} and the ratio in _{[(F I-1 / F} S) × 100 (%)] is less than 70% 0% and 2mm square of the outermost surface _{Ratio of silicon atomic weight [SI-1} ] on _{the surface to the above [SS} ] [(SI _-1 / _SS ) × 100 after etching the range of 5 kV with an argon gas cluster ion gun for 1 minute. (%)] Is 20% or more and 70% or less. The surface protection resin member according to claim 1, wherein the silicone resin is a silicone resin having two functional groups in one molecular structure. 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 according to claim 1 or 2. The surface protective resin member 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 surface protective resin member according to any one of claims 1 to 3, which is 30% or more and 60% or less. The ratio of the the highest fluorine atom amount at 2mm square surface after 20 minutes etching with argon gas cluster ion gun output 5kV range of the outer surface _{[F I-20] [F} S] [(F I- _{20 / F S) × 100 (} %)] is not more than 40% 0% and the silicon on the outermost surface 2mm square surface after 20 minutes etching with argon gas cluster ion gun output 5kV a range of atomic weight _{[S I-20]} with the _{[S S]} with any ratio of _{[(S I-20 / S} S) × 100 (%)] is less than 40% 0% claims 1 to 4 The surface protective resin member according to item 1. Claim that the molar ratio [OH _A / OH _P ] of the amount of total hydroxyl groups [OH _A ] in the acrylic resin and the amount of total hydroxyl groups [OH _P ] in the polyol is 0.1 or more and 4 or less. The surface protective resin member according to any one of 1 to 5. The surface protective resin member according to any one of claims 1 to 6, 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. 23 Martens hardness at ° C. is 0.5 N / mm ² or more 220 N / mm ² or less, and the return rate at 23 ° C. is 100% or less to 70% or more according to any one of claims 1 to 7 Surface protection resin member. With respect to 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, and an isocyanate group. A first solution containing a silicone resin having a plurality of reactive functional groups,
A second solution containing polyfunctional isocyanate and
A solution set for forming a surface protective resin member containing
The first fluorine atom amount at the outermost surface of the cured product of the mixture of solution and the second solution [F _S] is less 12 atm% or more 22 atm%, and the silicon atom content in the outermost surface [S _S] is or less 2 atm% or more 6 atm%, wherein the fluorine atom amount at the outermost surface 2mm square surface after etching for 1 minute with argon gas cluster ion gun output 5kV a range of _{[F I-1] [F} S ] And the ratio [(FI _-1 / F _S ) x 100 (%)] is 0% or more and 70% or less, and the range of 2 mm square on the outermost surface is 1 with an argon gas cluster ion gun having an output of 5 kV. weight silicon atom ratio of the _{[S I-1]} and _{[S S] [(S I} -1 / S S) × 100 (%)] is 70% or less than 20% for min etched surface after A solution set for forming a surface protective resin member.