JP6526481B2 - Resin sheet for nailing and its manufacturing method - Google Patents

Description

  The present invention relates to a resin sheet for nailing and a method of manufacturing the same.

In a ball game machine, a nail for changing the falling direction of the game ball is punched into a plurality of holes (usually through holes) formed in the game board by NC (numerical control machining) processing or the like.
At present, veneer plywood is the main material for game boards used in ball and ball games.
In recent years, in order to enhance the entertainment properties of ball and ball games, a plate-like transparent resin sheet is used as the material of the game board, and a display panel such as a liquid crystal display panel and / or a lighting device such as an LED (light emitting diode) The configuration has been studied (patent documents 1 to 3 and the like).

Examples of transparent resins include carbonate resins and methacryl resins.
Since the carbonate-based resin sheet has a relatively low surface hardness, the carbonate-based resin sheet tends to be easily scratched by friction with the gaming balls or collision of the gaming balls.
Since the methacrylic resin sheet has a relatively high surface hardness, it is hard to be scratched even by friction with the game ball or collision of the game ball. However, general methacrylic resins have insufficient impact resistance, and there is a risk of resin cracking during nailing. Therefore, Patent Documents 4 and 5 disclose a resin sheet for a ball game machine having impact resistance improved by adding acrylic rubber particles to methacrylic resin in order to suppress resin cracking at the time of nailing. (Claim 1 of patent document 4 and claim 1 of patent document 5).

In a ball and ball game machine, a resin sheet is cut into a predetermined shape using a saw or the like, a cutting process is performed, a hole for nailing and a hole for attaching various game members are opened using a drill or the like. A drilling process, an outer shape process for adjusting the outer shape using a router or the like, and the like are performed.
In these processing steps, the friction heat generated when tools such as saws, drills, and routers contact the resin sheet partially melts the resin, generating burrs and the like on the machined surface and the appearance quality is degraded, or There is a risk that the resin will fuse.

  In Patent Document 6, 100 parts by mass of a methacrylic resin, and at least one or more compounds (X) selected from the group consisting of a hydrocarbon, a fatty acid, an aliphatic alcohol, a fatty acid ester, a fatty acid amide, and a metal soap are used. There are disclosed a methacrylic resin composition containing 01 to 5 parts by mass and a methacrylic resin sheet using the same (claims 1 and 9).

  The compound (X) described in Patent Document 6 is a lubricant, and suppresses the frictional heat between the resin sheet and the tool by the lubricating effect to suppress the decrease in the appearance quality of the machined surface of the resin sheet and the resin fusion to the tool. (Paragraph 0027).

JP, 2000-061047, A Japanese Patent Application Laid-Open No. 07-000614 JP, 2005-034606, A JP, 2006-320705, A JP, 2008-049137, A International Publication No. 2014/156032

In Patent Document 6, as the application of the methacrylic resin sheet, a protective sheet for a display device or a signboard, a transparent roof member such as a car port, and a lighting fixture cover are specifically mentioned (paragraph 0049). There is no particular mention of nailing applications such as gaming machines.
In nailing applications such as ball and ball game machines, when a lubricant is added to a resin sheet, the nails that are driven in tend to loosen or come off easily.
As described above, in the ball and ball game machine, in recent years, a configuration in which a transparent resin sheet is combined with a display panel such as a liquid crystal display panel and / or an illumination device such as an LED (light emitting diode) has been studied. In such a configuration, the transparent resin sheet is exposed to a temperature of 40 ° C. or more by heat generated from the backlight of the liquid crystal display panel or the LED (light emitting diode).
In a temperature environment of 40 ° C. or higher, the lubricant added to the resin sheet tends to bleed out to the surface, so-called bleed out phenomenon tends to occur, and the problem of loosening or dropping of the driven nail becomes remarkable. If the bleed out phenomenon occurs, the sheet surface may be sticky.
If the amount of lubricant is reduced, although the bleed out phenomenon can be suppressed, there is a possibility that the lubricating effect may be insufficient.

  Patent Document 6 does not disclose the usage of a lubricant suitable for nailing applications such as ball and ball games. In addition, Patent Document 6 does not disclose the use amount of a suitable lubricant in a temperature environment of 40 ° C. or higher.

  The present invention has been made in view of the above circumstances, and a good lubricating effect is obtained, and the frictional heat between the resin sheet and the tool is suppressed to reduce the appearance quality of the machined surface of the resin sheet and the resin to the tool. It is an object of the present invention to provide a resin sheet for nailing which can suppress fusion and can stably suppress loosening or removal of a driven nail even in a temperature environment of 40 ° C. or higher. I assume.

The resin sheet for nailing of the present invention is
At least one lubricant mainly composed of at least one resin, having a melting point of 45 to 100 ° C., and selected from the group consisting of hydrocarbons, fatty acids, fatty alcohols, fatty acid esters, fatty acid amides, and metal soaps ( It consists of a resin composition containing 0.01-0.3 mass% of X),
Thickness is 5 mm or more,
It is used under an environment of 40 ° C or higher.

The method for producing a resin sheet for nailing of the present invention is
It is a manufacturing method of resin sheet for nailing of the above-mentioned this invention,
A step (1) of preparing the resin composition by melt-kneading a plurality of types of raw materials containing at least one of the above-mentioned resins as main components and a lubricant (X);
And (2) extruding the resin composition.

In the present specification, “main component” is defined as a component of 50% by mass or more.
As used herein, a "sheet" is a non-flexible plate.
In the present specification, “a lubricant” is a component that imparts lubricity to a resin sheet to reduce the coefficient of friction of the resin sheet.

In the present specification, “weight average molecular weight (Mw) and number average molecular weight (Mn)” are values obtained by converting a chromatogram measured by gel permeation chromatography (GPC) into the molecular weight of standard polystyrene.
As used herein, "molecular weight distribution" is defined by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), ie, Mw / Mn.
In the present specification, the content of the component having a molecular weight of 200,000 or more (defined as “high molecular weight component”) is a molecular weight of 200,000 among the area of a portion surrounded by a chromatogram and a baseline measured by GPC. Calculated as a percentage of the area of the retention time part earlier than the retention time of standard polystyrene.
The content of the component having a molecular weight of less than 15,000 (defined as "low molecular weight component") is based on the retention time of standard polystyrene having a molecular weight of 15,000, of the area of the portion enclosed by the chromatogram and baseline obtained by GPC. Calculated as a percentage of the area of the late retention time portion.

Specifically, the contents of weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), high molecular weight component and low molecular weight component are measured by the following methods.
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) are calculated by measuring a chromatogram with gel permeation chromatography (GPC) under the following conditions, and converting them into the molecular weight of standard polystyrene.
"HLC-8320" manufactured by Tosoh Corporation was used as a GPC apparatus. A differential refractive index detector (RI detector) is used as a detector. As a column, what connected "TSKgel Super Multipore HZM-M" 2 made by Tosoh Corp. and "Super HZ4000" in series is used. Tetrahydrofuran (THF) is used as an eluent. A solution of 4 mg of resin in 5 ml of tetrahydrofuran is used as a measurement sample. The eluent flow rate is 0.35 ml / min. The column temperature is 40 ° C. 20 μl of sample solution is injected at an eluent flow rate of 0.35 ml / min and the chromatogram is measured.
The baseline of the chromatogram is that the slope of the high molecular weight peak on the GPC chart changes from zero to positive as viewed from the earlier retention time, and the slope of the low molecular weight peak as viewed from the earlier retention time And a line connecting points that change from minus to zero. When the chromatogram shows multiple peaks, a line connecting the point where the slope of the peak on the high molecular weight side changes from zero to plus and the point where the slope of the peak on the low molecular weight side changes from negative to zero Make it a baseline.
From the integral molecular weight distribution calculated using the calibration curve, the ratio of components having a molecular weight of 200,000 or more (high molecular weight components) and the ratio of components having a molecular weight of less than 15,000 (low molecular weight components) are calculated.
GPC measurement is carried out using standard polystyrene having a molecular weight in the range of 400 to 5,000,000, and a calibration curve showing the relationship between the retention time and the molecular weight is prepared. A calibration curve is prepared using data of 10 standard polystyrenes.

In the present specification, unless otherwise specified, the "glass transition temperature (Tg)" is the midpoint glass transition temperature measured by the following method.
The sample was once heated to 230 ° C. and cooled to room temperature using a differential scanning calorimeter (“DSC-50” manufactured by Shimadzu Corporation), and then the temperature rising rate from room temperature to 230 ° C. again by 10 ° C./min. Measure the DSC curve under the conditions of temperature rise. An intermediate point determined from the obtained DSC curve is defined as a glass transition temperature (Tg). When a plurality of shoulders appear in the DSC curve, the glass transition temperature (Tg) is determined based on the shoulder on the highest temperature side.

  ADVANTAGE OF THE INVENTION According to this invention, a favorable lubricating effect is acquired and the frictional heat of a resin sheet and a tool can be suppressed, and the fall of the appearance quality of the processing surface of a resin sheet and resin fusion to a tool can be suppressed. And, even under a temperature environment of 40 ° C. or more, it is possible to provide a resin sheet for nailing which can stably suppress the loosening or removal of the driven nail.

It is a schematic diagram which shows the manufacturing apparatus of the resin sheet of one Embodiment which concerns on this invention.

"Resin sheet for nailing"
The present invention relates to a resin sheet for nailing (hereinafter sometimes simply referred to as "resin sheet").
The nailing application is not particularly limited, and includes, for example, a ball and ball game machine.
In a ball game machine, a nail for changing the falling direction of the game ball is punched into a plurality of holes (usually through holes) formed in the game board by NC (numerical control machining) processing or the like.
Other nailing applications include building materials such as resin sash and joint materials.

The resin sheet for nailing of the present invention is composed of a resin composition (C) containing at least one resin as a main component.
In the present invention, the resin composition (C) contains at least one lubricant (X) selected from the group consisting of hydrocarbons, fatty acids, fatty alcohols, fatty acid esters, fatty acid amides, and metal soaps.

The resin sheet for nailing of the present invention has a thickness of 5 mm or more.
If the thickness is less than 5 mm, the nail is easily removed. The thickness is preferably 8 mm or more.
On the other hand, if the thickness is too large, the resin sheet will be heavy and handling will be reduced, so 30 mm or less is preferable, 25 mm or less is more preferable, and 20 mm or less is particularly preferable.

The resin sheet for nailing of the present invention is used under a temperature environment of 40 ° C. or higher.
For example, in a ball and ball game machine, in recent years, a configuration in which a transparent resin sheet is combined with a display panel such as a liquid crystal display panel and / or an illumination device such as an LED (light emitting diode) has been studied. In such a configuration, the resin sheet is exposed to a temperature of 40 ° C. or more by the heat generated from the backlight of the liquid crystal display panel or the LED (light emitting diode).

(Main component resin)
The main component resin is not particularly limited, and is preferably a thermoplastic resin because it is excellent in moldability and productivity.
In applications such as ball and ball game machines, transparent resins such as methacrylic resins (A) and carbonate resins are preferred.
The methacrylic resin (A) is particularly preferable because it has a relatively high surface hardness and is not easily scratched even by friction with a game ball or collision of a game ball.

The methacrylic resin (A) is a resin containing at least one monomer unit derived from a methacrylic acid ester.
The methacrylic resin (A) preferably contains a monomer unit derived from methyl methacrylate (MMA).
In the methacrylic resin (A), the content of monomer units derived from methyl methacrylate (MMA) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, particularly preferably 90 And 100% by mass.
The methacrylic resin (A) can optionally contain one or more monomer units in addition to the monomer units derived from methyl methacrylate (MMA).

As other monomer units other than the monomer unit derived from methyl methacrylate (MMA), for example,
(Meth) acrylic acid alkyl esters such as methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid aryl esters such as phenyl (meth) acrylic acid;
(Meth) acrylic acid cycloalkyl esters such as (meth) acrylic acid cyclohexyl and norbornenyl (meth) acrylic acid;
and,
Monomer units derived from vinyl monomers having a polymerizable carbon-carbon double bond in one molecule such as (meth) acrylamide and (meth) acrylonitrile can be mentioned.

The weight average molecular weight (Mw) of the methacrylic resin (A) is preferably 50,000 to 300,000, more preferably 52,000 to 250,000, and particularly preferably 55,000 to 2,000,000.
The methacrylic resin (A) preferably has an average polymerization degree of 500 to 3,000, more preferably 520 to 2,500, and particularly preferably 550 to 2,000.
When the Mw and average polymerization degree of the methacrylic resin (A) are in the above ranges, mechanical properties such as toughness and impact resistance are good, and a sheet having uniform thickness and excellent surface smoothness is easily obtained.

The methacrylic resin (A) preferably has a molecular weight distribution (Mw / Mn) of 1.2 to 2.0, more preferably 1.3 to 1.7.
When the molecular weight distribution (Mw / Mn) is in the above range, mechanical properties such as toughness and impact resistance are good, and it is easy to obtain a sheet having excellent surface smoothness.

The content of the component (high molecular weight component) having a molecular weight of 200,000 or more is preferably 0.1 to 10%, and more preferably 0.5 to 5% in the methacrylic resin (A).
The content of the component (low molecular weight component) having a molecular weight of less than 15,000 is preferably 0.2 to 5%, and more preferably 1 to 4.5%.
When the content of the high molecular weight component and the low molecular weight component of the methacrylic resin (A) is in the above range, molding processability is improved and a sheet having a uniform thickness is easily obtained.

  From the viewpoint of molding processability, the methacrylic resin (A) preferably has a melt flow rate (MFR) of 0.1 g / m according to JIS K 7210 and measured at 230 ° C. under a load of 3.8 kg. 10 minutes or more, more preferably 0.1 to 30 g / 10 minutes, particularly preferably 0.5 to 20 g / 10 minutes, and most preferably 1.0 to 10 g / 10 minutes.

From the viewpoint of molding processability, the glass transition temperature (Tg) of the methacrylic resin (A) is preferably 100 ° C. or more. The upper limit of the glass transition temperature (Tg) of the methacrylic resin (A) is usually 130 ° C. or less.
The glass transition temperature (Tg) can be controlled by adjusting the molecular weight and the like.

The method for producing the methacrylic resin (A) is not particularly limited, and known polymerization methods such as radical polymerization method and anion polymerization method can be applied.
From the viewpoint of obtaining a methacrylic resin having high thermal decomposition resistance, few foreign matter, and high transparency, solvent-free continuous radical polymerization, anionic polymerization method and the like are preferable.
In the above-mentioned known polymerization method, Mw, the ratio of high molecular weight components, and low molecular weight components by adjusting the polymerization temperature, polymerization time, kind or amount of chain transfer agent, or kind or amount of polymerization initiator, etc. A methacrylic resin (A) can be produced in which the characteristics such as the ratio are in the desired range.

(Lubricant (X))
In applications such as ball and ball game machines, cutting process for cutting a resin sheet into a predetermined shape using a saw or the like with respect to a resin sheet for nailing, holes for nailing and various game members using a drill or the like A hole forming process for forming a mounting hole and an outer shape process for adjusting the outer shape using a router or the like are performed.
The lubricant (X) is a component that imparts lubricity to the resin sheet to reduce the coefficient of friction of the resin sheet, and the addition of this component makes it possible to lubricate the resin sheet in processing such as cutting or drilling. By suppressing the frictional heat between the resin sheet and the tool, it is possible to suppress the deterioration of the appearance quality of the machined surface of the resin sheet and the resin fusion to the tool.

  In general, lubricants include hydrocarbons, fatty acids, fatty alcohols, fatty acid esters, fatty acid amides, metal soaps and the like.

  In general, aliphatic hydrocarbons are preferable as hydrocarbons used as a lubricant. Aliphatic hydrocarbons include liquid paraffin, microcrystalline wax, natural paraffin, synthetic paraffin, and polyolefin wax. Aliphatic hydrocarbons having an average carbon number of 12 or more are preferred. The hydrocarbon may be an aliphatic hydrocarbon partial oxide or halide.

Generally, as a fatty acid used as a lubricant, lauric acid (melting point: 44 to 46 ° C.), palmitic acid (melting point: 63 ° C.), stearic acid (melting point: 69.9 ° C.), behenic acid (melting point: 74 to 78 ° C. C12 or more fatty acids such as oleic acid (melting point: 16 ° C.) and erucic acid (melting point: 33.8 ° C.) are preferred.
Among the above, fatty acids having 16 to 24 carbon atoms such as palmitic acid, stearic acid, behenic acid, oleic acid, and erucic acid are more preferable, and saturated C16 to 24 carbon atoms such as palmitic acid, stearic acid, and behenic acid Fatty acids are particularly preferred.
As a fatty acid, fatty acids having a hydroxyl group such as hydroxyl stearic acid are also preferable.
As a fatty acid, what is contained in fats and oils, such as animal oil, vegetable oil, and mineral wax, may be used. Animal oils include beef tallow, fish oil and the like. Vegetable oils include coconut oil, soybean oil, rapeseed oil, and rice bran wax. Mineral waxes include montan wax, ozokerite, ceresin, oil shells and the like.

Generally, as an aliphatic alcohol used as a lubricant, lauryl alcohol (melting point: 24 ° C.), cetanol (melting point: 49 ° C.), stearyl alcohol (melting point: 59-60 ° C.), and oleyl alcohol (melting point: 2 to 2) Aliphatic alcohols having 12 to 18 carbon atoms such as 7 ° C) are preferred.
Among the above, saturated aliphatic alcohols having 12 to 18 carbon atoms such as lauryl alcohol, cetanol and stearyl alcohol are more preferable,
Cetanol and saturated aliphatic alcohols having 16 to 18 carbon atoms such as stearyl alcohol are particularly preferred.
Such aliphatic alcohol may be contained in the above-mentioned oils and fats such as animal oil, vegetable oil and mineral wax.

Generally, as a fatty acid ester used as a lubricant, an ester (including a partial ester) of the above fatty acid and a monohydric or polyvalent (divalent or more) alcohol containing the above aliphatic alcohol is preferable.
The fatty acid is preferably a saturated fatty acid, and the alcohol is preferably a saturated alcohol.
As alcohol,
Butanol (melting point: -90 ° C), lauryl alcohol (melting point: 24 ° C), cetanol (melting point: 49 ° C), stearyl alcohol (melting point: 59-60 ° C), behenyl alcohol (melting point: 67-73 ° C), and oleyl alcohol Monohydric alcohols such as (melting point: 2 to 7 ° C.);
And polyhydric alcohols such as ethylene glycol (melting point: -12.6 ° C.), glycerin (melting point: 17.8 ° C.), and sorbitol (melting point: 95 ° C.).
As a fatty acid ester, the partial ester of the said fatty acid and the said polyhydric alcohol is preferable, and the fatty acid monoglyceride which is a partial ester of a C16-C22 fatty acid and glycerol is more preferable.

  In general, fatty acid amides used as lubricants include amides and bisamides of the above fatty acids. As such fatty acid amides, lauric acid amide (melting point: 87 ° C.), palmitic acid amide (melting point: 100 ° C.), stearic acid amide (melting point: 101 ° C.), behenic acid amide (melting point: 110 ° C.), hydroxystearic acid amide (Melting point: 107 ° C), oleic acid amide (melting point: 75 ° C), erucic acid amide (melting point: 81 ° C), N-oleylpalmitic acid amide (melting point: 68 ° C), N-stearylstearic acid amide (melting point: 95) ° C), N-stearyl oleic acid amide (melting point: 67 ° C.), N-oleyl stearic acid amide (melting point: 74 ° C.), N-stearylerucic acid amide (melting point: 69 ° C.), methylol stearic acid amide (melting point: 110) C., methylenebisstearic acid amide (melting point: 142 ° C), methylenebiscapric acid amide (melting point: 161 ° C), ethylenebis lauric acid amide (melting point: 157 ° C), and the like.

Generally, examples of metal soaps used as lubricants include alkaline earth metal salts or typical metal salts of the above-mentioned fatty acids.
As such metal soaps, barium stearate (melting point: 115 ° C. or higher), calcium stearate (melting point: 147 to 149 ° C.), magnesium stearate (melting point: 200 ° C. or more), zinc stearate (melting point: 128 to 130 ° C.) And aluminum stearate (melting point: 103 ° C.) and the like.

  In the present invention, as the lubricant (X), one or two or more lubricants having a melting point of 45 to 100 ° C. can be selected from the lubricants exemplified above.

As described above, by adding the lubricant (X) to the resin composition (C), the friction heat between the resin sheet and the tool is suppressed by the lubricating effect in processing such as cutting or drilling of the resin sheet for nailing As a result, it is possible to suppress the deterioration in the appearance quality of the machined surface of the resin sheet and the resin fusion to the tool.
However, when the amount of the lubricant (X) in the resin composition (C) is too large, in the nailing application such as a ball and ball game machine, the driven nail tends to be easily loosened or dropped.
In the ball and ball game machine, in recent years, a configuration in which a transparent resin sheet is combined with a display panel such as a liquid crystal display panel and / or an illumination device such as an LED (light emitting diode) has been studied. In such a configuration, the transparent resin sheet is exposed to a temperature of 40 ° C. or more by heat generated from a backlight of the liquid crystal display panel or an LED (light emitting diode).
In a temperature environment of 40 ° C. or higher, the lubricant added to the resin sheet is likely to cause so-called bleed-out phenomenon that oozes to the surface, and the problem of loosening or dropping out of the nail that has been driven in becomes noticeable. When the bleed out phenomenon occurs, there is also a problem that stickiness occurs on the sheet surface.

In the resin sheet for nailing of the present invention, the content of the lubricant (X) in the resin composition (C) is 0.01 to 0.3% by mass.
When the content of the lubricant (X) in the resin composition (C) is less than 0.01% by mass, the lubricating effect is insufficient, and the resin sheet and the tool are processed in processing such as cutting or drilling of the resin sheet for nailing The friction heat of the resin sheet can not be stably suppressed, and the appearance quality of the machined surface of the resin sheet may be deteriorated and the resin may be fused to the tool.
If the content of the lubricant (X) in the resin composition (C) is more than 0.3% by mass, the nails used in ballistic ball games, etc. There is a risk of loosening or missing.
By setting the content of the lubricant (X) in the resin composition (C) to 0.01 to 0.3% by mass, the friction heat between the resin sheet and the tool is suppressed, and the appearance of the processed surface of the resin sheet It is possible to suppress the deterioration of the quality and the resin fusion to the tool, and it is possible to stably suppress the loosening or removal of the driven nail even under an environmental temperature of 40 ° C. or higher.

The melting point of the lubricant (X) is 45 to 100 ° C., preferably 50 to 70 ° C., because the bleed out under an environmental temperature of 40 ° C. or more can be effectively suppressed.
When the melting point of the lubricant (X) is less than 45 ° C., the lubricant (X) tends to bleed out on the sheet surface at a temperature of 40 ° C. or higher, and the nails that are driven in tend to loosen or come out easily.
When the melting point of the lubricant (X) is 100 ° C. or more, the lubricating effect becomes insufficient, and in the processing such as cutting or drilling of the resin sheet for nailing, the frictional heat between the resin sheet and the tool can be stably suppressed. In addition, the appearance quality of the machined surface of the resin sheet may be degraded and resin fusion to the tool may occur.

The lubricant (X) preferably contains a fatty acid ester and / or a fatty alcohol because it has a relatively high melting point, is less likely to bleed out, and can exhibit a good lubricating effect.
Here, as fatty acid ester, fatty acid monoglyceride which is a partial ester of a C16-C22 fatty acid and glycerin is preferable.
As aliphatic alcohol, C12-C18 aliphatic alcohol is preferable.

As the fatty acid monoglyceride, for example, stearic acid monoglyceride is preferable. Stearate monoglyceride has a melting point of about 65 ° C., is difficult to bleed out at a temperature of 40 ° C. or higher, and exerts a good lubricating effect in processing such as cutting or punching of a resin sheet for nailing .
As the aliphatic alcohol, for example, cetanol and stearyl alcohol are preferable. They have a melting point of about 50 to 60 ° C., and are hard to bleed out at a temperature of 40 ° C. or more, and exhibit a good lubricating effect in processing such as cutting or punching of a resin sheet for nailing.

It is preferred to use a plurality of lubricants (X) having different melting points within the range of 45-100 ° C. The melting points of the plurality of lubricants (X) preferably differ by 5 ° C. or more.
In the case of using a plurality of lubricants (X) having different melting points, a lubricating effect can be exhibited within a wider temperature range in processing such as cutting or drilling of a resin sheet for nailing, which is preferable.

As described above, in the present invention, one or two or more lubricants (X) having a melting point of 45 to 100 ° C. are used.
However, without departing from the spirit of the present invention, it is acceptable to use a lubricant (Y) having a melting point of less than 45 ° C. and / or a lubricant (Z) having a melting point of more than 100 ° C. in small amounts.
Even when a lubricant (X) is mainly used as a lubricant and a small amount of lubricant (Y) and / or lubricant (Z) is used in combination, the lubricant bleeds out on the sheet surface, and the loosening or removal of the driven nail due to this. It can be suppressed.
The combined use amount of the lubricant (Y) having a melting point of less than 45 ° C. and / or the lubricant (Z) having a melting point of more than 100 ° C. is effective because the effects by the use of the lubricant (X) are effectively exhibited Is preferably less than 0.1% by mass, and more preferably 0.05% by mass or less.

(Acrylic rubber (B))
In the resin sheet for nailing of the present invention, when the main component resin is a methacrylic resin (A), the resin composition (C) preferably further contains an acrylic rubber (B).
Acrylic rubber (B) can improve the impact resistance of the resin sheet for nailing, and can suppress resin cracking at the time of nailing.
The acrylic rubber (B) is not particularly limited, and examples thereof include multilayer structure particles (BX) including at least one rubber layer, and a block copolymer (BY).
It is preferable that the acrylic rubber (B) contains multilayer structure particles (BX), because the effect of improving the impact resistance can be obtained effectively.

<Multilayer structured particle (BX)>
The multilayer structured particle (BX) including at least one rubber layer is an acrylic rubber particle having a so-called core-shell structure including a soft layer (rubber layer) and a hard layer.

If the amount of addition of the multilayer structure polymer (BX) is too small, the effect of improving the impact resistance can not be obtained effectively, and there is a possibility that resin cracking may occur at the time of nailing.
When the addition amount of the multilayer structure polymer (BX) is excessive, the surface smoothness and the surface hardness of the resin sheet may be reduced.
The content of the multilayer structure polymer (BX) in the resin composition (C) is preferable because the effect of improving the impact resistance is effectively obtained and the surface smoothness and the surface hardness of the resin sheet become good. Is 15% by mass or more, more preferably 15 to 45% by mass, still more preferably 15 to 30% by mass, particularly preferably 18 to 30% by mass, and most preferably 20 to 30% by mass.

In the present specification, unless otherwise specified, the content of the multilayer structure polymer (BX) is measured as follows.
After one piece of the resin sheet is sufficiently dried to remove moisture, its mass (W1) is measured.
Next, the sheet piece is placed in a test tube, and acetone is added thereto for dissolution to remove the acetone soluble portion.
The acetone is then removed using a vacuum heat dryer and the mass of the residue (W2) is determined.
Based on the following formula, the content of the multilayer structure polymer (BX) is determined.
[Content of Multi-Layer Structure Polymer (BX)] = (W2 / W1) × 100 (%)

  In addition, when the outermost layer of a multilayer structure polymer (BX) melt | dissolves in acetone, the compounding quantity of multilayer structure polymer (BX) and the content calculated | required by the said measurement may not correspond. However, in the present specification, the content of the multilayer structure polymer (BX) is determined by regarding the acetone insoluble portion as a rubber component contributing to the impact resistance.

If the particle size of the multilayer structure polymer (BX) in the sheet is too small, the impact resistance improvement effect can not be effectively obtained, and there is a risk that resin cracking may occur at the time of nailing.
If the particle size of the multilayer structure polymer (BX) in the sheet is too large, particularly if the amount of the multilayer structure polymer (BX) added is large, the driven nail tends to come off easily.
The particle diameter of the multilayer structure polymer (BX) in the sheet is preferably 0.05 to 0.3 μm, since the effect of improving the impact resistance is effectively obtained and nail penetration is suppressed.

In the present specification, unless otherwise specified, the particle diameter of the polymer particles in the latex containing the polymer particles is measured using a light scattering photometer DLS-600 manufactured by Otsuka Electronics Co., Ltd.
The average particle size of the polymer particles in the latex is measured by the dynamic light scattering method using a sample collected from the latex after completion of polymerization, analyzed by the cumulant method, and determined.

In the process of sheet production, the non-crosslinked outermost layer of the multilayer structure polymer (BX) may be melted to form a matrix. In this case, the particle size of the multilayer structure polymer (BX) in the sheet is smaller than the particle size of the polymer particles of the raw material.
In the present specification, unless otherwise specified, the particle diameter of the multilayer structure polymer (BX) in the sheet is determined by cross-sectional observation with a transmission electron microscope (TEM).
Specifically, a part of the resin sheet is cut out, cut in the thickness direction with a microtome under freezing conditions, and the obtained section is stained with ruthenium acid, and then the cross section of the dyed rubber particles is observed by TEM. . The average value of 100 particles is taken as the average particle size.

As a multilayer structure polymer (BX),
The outermost layer is a hard layer comprising 40 to 100% by mass of at least one methacrylic acid ester unit, and optionally 0 to 60% by mass of other copolymerizable monomer units,
40 to 99.9% by mass of at least one type of acrylic acid ester unit, and 0 to 60% by mass of other monomer units that can be copolymerized as needed, at least one inner layer (layer inside the outermost layer) And the multilayer structure polymer (BX-1) which is a soft layer (rubber layer) containing 0.1-5 mass% of polyfunctional monomer units is preferable.

  In the present specification, the "polyfunctional monomer" is a crosslinking agent (crosslinkable monomer) containing two or more polymerizable functional groups.

  The hard layer constituting the outermost layer of the multilayer structure polymer (BX-1) has a glass transition temperature (Tg) of 25 ° C. or higher when the layer is formed alone from the viewpoint of heat resistance expression. Is preferred. In addition, at least one inner layer is formed of a soft layer (rubber layer), and in view of impact resistance expression, the glass transition temperature (Tg) when the soft layer is formed alone is less than 25 ° C. preferable.

  The proportion of the outermost layer in the acrylic multilayer structure particles (BX-1) is not particularly limited, but 10 to 80 mass in order to secure good dispersibility at the time of melt-kneading with the methacrylic resin (A). It is preferable to be in the range of%.

  From the viewpoint of transparency, methacrylic acid esters are used as monomers for the hard layer of the acrylic multilayer structure particles (BX-1), and examples thereof include methyl methacrylate, ethyl methacrylate and butyl methacrylate, Examples thereof include benzyl methacrylate and cyclohexyl methacrylate. These can be used alone or in combination of two or more. The methacrylic acid ester used for the hard layer preferably contains methyl methacrylate.

In the hard layer, if necessary, a copolymerizable unsaturated monomer and / or a polyfunctional monomer which is a crosslinking agent can be used in combination with the methacrylic acid ester.
As a copolymerizable unsaturated monomer,
Acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and benzyl acrylate;
Aromatic vinyl compounds such as styrene, vinyl toluene, and α-methylstyrene;
N-substituted maleimide compounds such as N-cyclohexyl maleimide, N-o-chlorophenyl maleimide, and N-tert-butyl maleimide;
Examples thereof include vinyl cyanide compounds such as (meth) acrylonitrile.
These can be used alone or in combination of two or more.

As a polyfunctional monomer,
Allyl (meth) acrylate, triallyl cyanurate, allyl cinnamate, allyl sorbate, diallyl maleate, diallyl phthalate, triallyl trimellitate, diallyl fumarate, ethylene glycol di (meth) acrylate, polyethylene glycol di ( Examples include meta) acrylate, divinylbenzene, and 1,3-butylene glycol di (meth) acrylate.
These can be used alone or in combination of two or more.

  As a monomer for the soft layer (rubber layer) of the acrylic multilayer structure particle (BX-1), from the point of impact resistance, acrylic acid ester, and other monomers which can be copolymerized if necessary And multifunctional monomers are used.

As acrylic acid ester, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, benzyl acrylate and the like can be mentioned.
These can be used alone or in combination of two or more.
The acrylic ester used for the soft layer (rubber layer) preferably contains butyl acrylate and / or 2-ethylhexyl acrylate.

As another monomer copolymerizable with acrylic acid ester,
Diene compounds such as 1,3-butadiene, 2,3-dimethyl butadiene and isoprene;
Aromatic vinyl compounds such as styrene, vinyl toluene, and α-methylstyrene;
Methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate;
Examples thereof include vinyl cyanide compounds such as (meth) acrylonitrile.
These can be used alone or in combination of two or more.

As polyfunctional monomers, allyl (meth) acrylate, triallyl cyanurate, allyl cinnamate, allyl sorbate, diallyl maleate, diallyl phthalate, triallyl trimellitate, diallyl fumarate, ethylene glycol di ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, divinyl benzene, and 1,3-butylene glycol di ( Meta) acrylate etc. are mentioned.
These can be used alone or in combination of two or more.

  The multilayer structure of the acrylic multilayer structure particle (BX-1) is optional as long as the outermost layer is a hard layer and at least one inner layer is a soft layer. As a multilayer structure, from the inner layer toward the outer layer, a two-layer structure of soft layer-hard layer, a three-layer structure of hard layer-soft layer-hard layer, soft layer-hard layer-soft layer-hard layer A four-layer structure of layers, and a four-layer structure of hard layer-soft layer-soft layer-hard layer, and the like can be mentioned.

The acrylic multilayer structured particle (BX-1) can be produced by a known emulsion polymerization method.
First, one or more types of raw material monomers are emulsion-polymerized to form core particles, and then one or more other monomers are emulsion-polymerized in the presence of the core particles to form core particles Form a shell around the. Then, if necessary, one or more monomers are further emulsion-polymerized in the presence of the core and shell particles to form another shell. By repeating such a polymerization reaction, it is possible to produce the objective acrylic multilayer structure particles (BX-1) as an emulsion latex.

For the emulsion polymerization, known surfactants can be used. The surfactant can be selected according to the purpose from the viewpoint of the stability of the polymerization system and the particle diameter of the acrylic multilayer structure particles to be produced.
As surfactant, anionic surfactant, cationic surfactant, and nonionic surfactant etc. are mentioned, Anionic surfactant is preferable.
These surfactants can be used alone or in combination of two or more.

As an anionic surfactant,
Carboxylates such as sodium stearate, sodium myristate, and sodium N-lauroyl sarcosinate;
Sulfonates such as sodium dioctyl sulfosuccinate and sodium dodecyl benzene sulfonate;
Sulfate ester salts such as sodium lauryl sulfate;
Examples thereof include phosphoric acid esters such as mono-n-butylphenyl pentaoxyethylene sodium phosphate and the like.

The polymerization initiator used for the emulsion polymerization is not particularly limited,
Inorganic peroxides such as potassium persulfate and ammonium persulfate;
Water-soluble redox initiators such as hydrogen peroxide-ferrous salt type, potassium persulfate-sodium acid sulfite type, and ammonium persulfate-sodium acid sulfite type;
Examples thereof include water-oil soluble redox initiators such as cumene hydroperoxide-sodium formaldehyde sulfoxylate, and tert-butyl hydroperoxide-sodium formaldehyde sulfoxylate.

A chain transfer agent can be used in the emulsion polymerization, if necessary.
Chain transfer agents include alkyl mercaptans such as n-dodecyl mercaptan, n-lauryl mercaptan, tert-dodecyl mercaptan, and sec-butyl mercaptan.

  During emulsion polymerization of each layer, addition of raw materials such as monomers, emulsifiers, polymerization initiators, and chain transfer agents to the polymerization reaction system may be any known methods such as batch addition method, split addition method, and continuous addition method. It can be done by the method.

  The polymerization reaction temperature of each layer is preferably 30 to 120 ° C., and more preferably 50 to 100 ° C. The polymerization reaction time of each layer varies depending on the type and amount of polymerization initiator and emulsifier used, and the amount used, but in each layer is usually 0.5 to 7 hours. The mass ratio of the monomer to water (monomer / water) is preferably 1/20 to 1/1.

The acrylic multilayer structure particles (BX-1) contained in the polymer latex obtained by emulsion polymerization are granular. The particle diameter is preferably 0.05 to 0.3 μm.
A latex containing acrylic multilayer structured particles (BX-1) can be used for the production of a sheet.
The acrylic multilayer structured particles (BX-1) are optionally subjected to coagulation, dehydration, drying and the like by a known method on a polymer latex produced by emulsion polymerization to obtain a powdery polymer. It can be collected as

(Block copolymer (BY))
The block copolymer (BY) is not particularly limited, and a block copolymer (BY-1) containing a methacrylic acid ester polymer block (b1) and an acrylic acid ester polymer block (b2) is preferred.
The number of methacrylic acid ester polymer blocks (b1) in the block copolymer (BY) is not particularly limited, and may be singular or plural.
Similarly, the number of acrylic acid ester polymer blocks (b2) in the block copolymer (BY) is not particularly limited, and may be singular or plural.
The acrylic rubber (B) can contain one or more block copolymers (BY).

The methacrylic acid ester polymer block (b1) is a polymer block containing a structural unit (methacrylic acid ester unit) derived from a methacrylic acid ester.
The proportion of methacrylic acid ester units in the methacrylic acid ester polymer block (b1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more is there.

It does not restrict | limit especially as said methacrylic acid ester.
For example, methyl methacrylate (MMA), ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, methacryl Isoamyl acid, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate And 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate.
The methacrylic acid ester polymer block (b1) can be formed by polymerizing one of these methacrylic acid esters alone or in combination of two or more.
Among the above-mentioned methacrylic acid esters, methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, from the viewpoint of improving the transparency and heat resistance, etc. And methacrylic acid alkyl esters such as isobornyl methacrylate are preferable, and methyl methacrylate (MMA) and the like are particularly preferable.

The methacrylic acid ester polymer block (b1) may contain structural units derived from monomers other than methacrylic acid esters.
The proportion of structural units derived from monomers other than methacrylic acid ester contained in the methacrylic acid ester polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass The content is particularly preferably in the range of 2% by mass or less.

It does not restrict | limit especially as monomers other than methacrylic acid ester.
For example, acrylic ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride and the like Can be mentioned.
These monomers other than methacrylic acid ester can form methacrylic acid ester polymer block (b1) by copolymerizing together with the above-mentioned methacrylic acid ester individually by 1 type or in combination of 2 or more types.

Methacrylic acid ester polymer block (b1) is preferably formed of a polymer having a refractive index _{(n 23D)} is in the range of 1.485 to 1.495. By this, the transparency of a resin composition (C) can be made favorable.

In the present specification, “refractive index (n _23D )” means a value measured at a measurement wavelength of 587.6 nm (d line) under an environment of 23% with a relative humidity (RH) of 50%.

The weight average molecular weight Mw (b1) of the methacrylic acid ester polymer block (b1) is preferably 5000 to 150,000, more preferably 8,000 to 120,000, and particularly preferably 12,000 to 100,000.
When the block copolymer (BY) contains a plurality of methacrylic acid ester polymer blocks (b1), the above-mentioned weight average molecular weight Mw (b1) corresponds to each of all the methacrylic acid ester polymer blocks (b1). The weight average molecular weight of is calculated and defined as the sum of the values.

  When the block copolymer (BY) contains a plurality of methacrylic acid ester polymer blocks (b1), the composition and molecular weight of the structural units constituting each methacrylic acid ester polymer block (b1) may be the same or not. Good.

Let the weight average molecular weight (Mw) of methacrylic resin (A) be "Mw (A)."
In the resin composition (C), Mw (A) / Mw (b1) is preferably 0.5 to 5.0, more preferably 1.0 to 4.0, and particularly preferably 1.2 to 3.0. is there.
If Mw (A) / Mw (b1) is too small, the impact resistance of the resin sheet for nailing tends to decrease.
On the other hand, when Mw (A) / Mw (b1) is excessive, the surface smoothness and transparency of the resin sheet for nailing tend to be deteriorated.
When Mw (A) / Mw (b1) is in the above range, the dispersed particle size of the block copolymer (BY) in the resin sheet for nailing becomes sufficiently small, and the surface smoothness and transparency are good. It becomes.

  The weight average molecular weight (Mw) of each block of the methacrylic acid ester polymer block (b1) and the acrylic acid ester polymer block (b2) is an intermediate product and final product in the process of producing the block copolymer (BY). It is calculated from the weight average molecular weight (Mw) of the block copolymer (BY) which is the product.

From the viewpoint of transparency, flexibility, moldability, surface smoothness, etc., the proportion of the methacrylic acid ester polymer block (b1) in the block copolymer (BY) is 10 to 80% by mass, preferably 20 to 20% by mass. 70 mass%, more preferably 40 to 60 mass%.
When the proportion of the methacrylic acid ester polymer block (b1) in the block copolymer (BY) is in the above range, the resin sheet for nailing becomes excellent in transparency and impact resistance.

The acrylic ester polymer block (b2) is a polymer block containing a structural unit (acrylic ester unit) derived from an acrylic ester.
The proportion of the acrylic ester unit in the acrylic ester polymer block (b2) is preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, particularly preferably 90% by mass or more .

As the above-mentioned acrylic ester, for example,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, acrylic acid n-hexyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-acrylate acrylate Methoxyethyl, glycidyl acrylate, allyl acrylate and the like can be mentioned.
The acrylic acid ester polymer block (b2) can be formed by polymerizing these acrylic acid esters singly or in combination of two or more.

  The acrylic ester polymer block (b2) may contain a structural unit derived from a monomer other than the acrylic ester. The proportion of structural units derived from monomers other than acrylic acid ester contained in the acrylic acid ester polymer block (b2) is preferably 55% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass The content is particularly preferably 10% by mass or less.

As monomers other than acrylic acid esters, methacrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, (meth) acrylonitrile, (meth) acrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride And vinylidene chloride and vinylidene fluoride.
These monomers other than acrylic acid ester can form acrylic acid ester polymer block (b2) by copolymerizing with above-mentioned acrylic acid ester individually by 1 type or in combination of 2 or more types.

  From the viewpoint of improving the transparency of the resin composition (C), etc., the acrylic acid ester polymer block (b2) is a non-aromatic structural unit derived from an acrylic acid ester having no aromatic ring (non-aromatic structural unit It is preferable to include an acrylic ester unit) and an aromatic structural unit (aromatic (meth) acrylic ester unit) derived from a (meth) acrylic ester having an aromatic ring.

Examples of non-aromatic acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dodecyl acrylate.
Among them, n-butyl acrylate, 2-ethylhexyl acrylate and the like are preferable.

The aromatic (meth) acrylic acid ester is obtained by ester bonding an aromatic ring or a group containing the same to (meth) acrylic acid.
Examples of such aromatic (meth) acrylic acid esters include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and styryl (meth) acrylate.
Among them, phenyl methacrylate, benzyl (meth) acrylate, phenoxyethyl methacrylate and the like are preferable.

  When the acrylic acid ester polymer block (b2) contains a nonaromatic acrylic acid ester unit and an aromatic (meth) acrylic acid ester unit, the acrylic acid ester polymer block (b2) is a nonaromatic acrylic acid ester unit It is preferable to contain 50 to 90% by mass and 50 to 10% by mass of aromatic (meth) acrylic acid ester units, and 60 to 80% by mass of nonaromatic acrylic acid ester units and aromatic (meth) acrylic acid ester unit 40 It is more preferable to contain -20 mass%.

Acrylate polymer block (b2) preferably configured in polymer refractive index _{(n 23D)} is in the range of 1.485 to 1.495. By this, the transparency of the resin sheet for nailing can be made favorable.

The weight average molecular weight Mw (b2) of the acrylic acid ester polymer block (b2) is preferably 5,000 to 120,000, more preferably 1,500 to 110,000, and particularly preferably 30,000 to 100,000.
In the case where the block copolymer (BY) contains a plurality of acrylic acid ester polymer blocks (b2), the above weight average molecular weight Mw (b2) is for all acrylic acid ester polymer blocks (b2) The weight average molecular weight of each is calculated and defined as the sum of the values.

  When there are a plurality of acrylic acid ester polymer blocks (b2) in the block copolymer (BY), the composition and molecular weight of the structural units constituting each acrylic acid ester polymer block (b2) may be the same or not. Good.

  If Mw (b2) is too small, the impact resistance of the resin sheet for nailing tends to decrease. On the other hand, when Mw (b2) is excessive, the surface smoothness and transparency of the resin sheet for nailing tend to be deteriorated.

From the viewpoint of transparency and surface smoothness, the proportion of the acrylic acid ester polymer block (b2) in the block copolymer (BY) is preferably 20 to 90% by mass, more preferably 30 to 80% by mass.
When the proportion of the acrylic ester polymer block (b2) in the block copolymer (BY) is within the above range, the resin sheet for nailing is excellent in impact resistance.

In the block copolymer (BY), the bonding form of the methacrylic acid ester polymer block (b1) and the acrylic acid ester polymer block (b2) is not particularly limited.
Examples of the bonding form include a structure in which a methacrylic acid ester polymer block (b1) and an acrylic acid ester polymer block (b2) are connected in series.
As a form of connection connected in series, for example,
One end of an acrylic acid ester polymer block (b2) is connected to one end of a methacrylic acid ester polymer block (b1) (a diblock copolymer of (b1)-(b2) structure);
Triblock copolymer of (b2)-(b1)-(b2) structure in which one end of acrylic acid ester polymer block (b2) is connected to both ends of methacrylic acid ester polymer block (b1) );
And triblock copolymer of (b1)-(b2)-(b1) structure in which one end of methacrylic acid ester polymer block (b1) is connected to each of both ends of acrylic acid ester polymer block (b2) And the like.

Other forms of bonding include
Block copolymer ([[(b1)-(b2)-] nX structure) in which one end of a plurality of block copolymers of (b1)-(b2) structure is connected to form a radial structure;
Block copolymer ([[(b2)-(b1)-] nX structure) in which one end of a plurality of block copolymers of (b2)-(b1) structure is connected to form a radial structure;
A block copolymer ([[(b1)-(b2)-(b1)-] nX) in which one end of a plurality of block copolymers having a (b1)-(b2)-(b1) structure is connected to form a radial structure Construction);
And a block copolymer ([(b2)-(b1)-(b2)-]) in which one end of the block copolymer having a plurality of (b2)-(b1)-(b2) structures is connected to form a radial structure. and star block copolymers such as nX structure).

  Other bonding forms include block copolymers having a branched structure.

  In addition, X in description of the said coupling form is a coupling agent residue.

  Among the bonding forms, a diblock copolymer, a triblock copolymer, and a star block copolymer are preferable, and a diblock copolymer having a (b1)-(b2) structure, (b1)-(b2) Triblock copolymer of (b1) structure, star block copolymer of [(b1)-(b2)-] nX structure, and [(b1)-(b2)-(b1)-] nX structure Star block copolymers are more preferred.

The block copolymer (BY) may have other polymer blocks (b3) other than the methacrylic acid ester polymer block (b1) and the acrylic acid ester polymer block (b2).
The main structural units constituting the other polymer block (b3) are structural units derived from monomers other than methacrylic acid esters and acrylic acid esters.
As such a monomer, for example,
Olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene;
Conjugated dienes such as butadiene, isoprene and myrcene;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene;
Examples include vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone and the like.
These can be used alone or in combination of two or more.

The bonding form of the methacrylic acid ester polymer block (b1), the acrylic acid ester polymer block (b2), and the polymer block (b3) in the block copolymer (BY) is not particularly limited.
As the bonding form, for example, a block copolymer of (b1)-(b2)-(b1)-(b3) structure, and (b3)-(b1)-(b2)-(b1)-(b3) structure Block copolymers and the like.
When there are a plurality of polymer blocks (b3) in the block copolymer (BY), the composition and molecular weight of the structural units constituting each polymer block (b3) may be the same or non-identical.

  The block copolymer (BY) may optionally have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, and an amino group in the molecular chain or at the molecular chain terminal.

Let the weight average molecular weight (Mw) of a block copolymer (BY) be "Mw (B)." Mw (B) is preferably 32000 to 300,000, more preferably 45000 to 230000.
If Mw (B) is too small, sufficient melt tension can not be maintained in melt extrusion molding, and a resin sheet for nailing is difficult to obtain, and mechanical properties such as breaking strength of the resin sheet for nailing obtained are There is a tendency to decline. On the other hand, when the Mw (B) is too large, the viscosity of the molten resin becomes high, which is attributed to the fine textured unevenness or unmelted substance (high molecular weight) on the surface of the resin sheet for nailing obtained by melt extrusion molding. However, there is a tendency that it is difficult to obtain a good resin sheet for nailing.

  The molecular weight distribution (Mw / Mn) of the block copolymer (BY) is preferably 1.0 to 2.0, more preferably 1.0 to 1.6. By having the molecular weight distribution (Mw / Mn) within such a range, the content of the unmelted material causing the generation of bumps in the resin sheet for nailing can be made extremely small.

Block copolymer refractive index of the _{(BY) (n 23D)} is preferably from 1.485 to 1.495, more preferably 1.487 to 1.493. When the refractive index (n _23D ) is in this range, the transparency of the resin sheet for nailing can be made good.

The method for producing the block copolymer (BY) is not particularly limited, and known methods can be used.
For example, a method of living polymerizing monomers constituting each polymer block is preferred.
As a method of living polymerization, for example,
Method of anionically polymerizing an organic alkali metal compound as a polymerization initiator in the presence of a mineral acid salt such as an alkali metal or alkaline earth metal salt;
Method of anionic polymerization in the presence of an organoaluminum compound using an organic alkali metal compound as a polymerization initiator;
Method of polymerization using an organic rare earth metal complex as a polymerization initiator;
and,
The method of radically polymerizing in presence of a copper compound etc. is mentioned using an alpha-halogenated ester compound as a polymerization initiator.
Moreover, the method etc. which are manufactured as a mixture containing block copolymer (BY) are also mentioned by polymerizing the monomer which comprises each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent. .
Among these methods, in particular, since the block copolymer (BY) is obtained with high purity, the control of the molecular weight and the composition is easy, and it is economical, the organic alkali metal compound is used as a polymerization initiator It is preferable to use an anionic polymerization method in the presence of an organoaluminum compound.

(Optional ingredient)
The resin sheet for nailing of the present invention can contain optional components other than the above as required.
The resin sheet for nailing of the present invention can contain one or more other resins.
The resin sheet for nailing of the present invention can contain one or more of various additives.

As other resin,
Olefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 and polynorbornene;
Ethylene ionomers;
Styrenic resins such as polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, AS resin, ABS resin, AES resin, AES resin, AAS resin, ACS resin, and MBS resin;
Ester-based resins such as polyethylene terephthalate and polybutylene terephthalate;
Amide-based resins such as nylon 6, nylon 66, and polyamide elastomers;
Halogen-containing resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polyvinylidene fluoride;
Acetal resin;
Urethane resin;
Modified polyphenylene ether, and polyphenylene sulfide;
Silicone modified resin;
Silicone rubber;
Styrenic thermoplastic elastomers such as SEPS, SEBS, and SIS;
And olefin rubbers such as IR, EPR, and EPDM.

  The amount of other resins that can be contained in the resin sheet for nailing of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably 0% by mass.

  Additives include UV absorbers, fillers, antioxidants, heat deterioration inhibitors, light stabilizers, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusing agents, organic dyes , Matting agents, and phosphors.

The ultraviolet light absorber is a compound having the ability to absorb ultraviolet light. UV absorbers are compounds that are said to mainly have the function of converting light energy into thermal energy.
Examples of UV absorbers include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, oxalic acid anilides, malonic esters, and formamidines.
One or more of these may be used.
Among the above, benzotriazoles, triazines, or ultraviolet absorbers having a maximum value ε _max of molar absorption coefficient at a wavelength of 380 to 450 nm of 1200 dm ³ · mol ⁻¹ cm ⁻¹ or less are preferable.

Benzotriazoles have a high effect of suppressing deterioration of optical characteristics such as coloring due to ultraviolet irradiation.
As benzotriazoles,
2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by BASF; trade name: TINUVIN 329),
2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by BASF; trade name: TINUVIN 234),
and,
Preferred is 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4-tert-octylphenol] (manufactured by Adeka; LA-31).

The ultraviolet absorber whose maximum value ε _max of the molar absorption coefficient at a wavelength of 380 to 450 nm is 1200 dm ³ · mol ^-1 cm ^-1 or less can suppress the yellowish taste of the obtained molded article. Examples of such UV absorbers include 2-ethyl-2'-ethoxy-oxalanilide (manufactured by Clariant Japan Co., Ltd .; trade name: Sanduibor VSU) and the like.

  Among the ultraviolet absorbers described above, benzotriazoles and the like are preferably used from the viewpoint of suppressing resin deterioration due to ultraviolet irradiation.

When it is desired to efficiently absorb a wavelength around 380 nm, a UV absorber of triazines is preferably used.
As such an ultraviolet absorber,
2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (manufactured by Adeka; LA-F70),
And hydroxyphenyl triazine based ultraviolet absorbers (BASF; TINUVIN 477-D and TINUVIN 460), which are analogs thereof, and the like.

In addition, maximum value (epsilon) _max of the molar absorption coefficient of a ultraviolet absorber is measured as follows.
Add 10.00 mg of a UV absorber to 1 L of cyclohexane, and dissolve it so that there is no undissolved matter by visual observation. This solution is injected into a 1 cm × 1 cm × 3 cm quartz glass cell, and the absorbance at a wavelength of 380 to 450 nm is measured using a U-3410 spectrophotometer manufactured by Hitachi, Ltd. The molar absorption coefficient maximum value ε _max is calculated from the molecular weight of the ultraviolet light absorber (M _UV ) and the maximum value of the measured absorbance (A _max ) according to the following equation.

ε _max = [A _max / (10 × 10 ^-3 )] × M _UV

The antioxidant has an effect of preventing oxidative deterioration of the resin alone in the presence of oxygen.
For example, phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants may be mentioned. One or more of these antioxidants can be used.
Among them, from the viewpoint of the effect of preventing deterioration of optical properties due to coloring, phosphorus-based antioxidants and hindered phenol-based antioxidants are preferable, and the combined use of phosphorus-based antioxidants and hindered phenol-based antioxidants is more preferable. .
When using a phosphorus-based antioxidant and a hindered phenol-based antioxidant in combination, the usage of the phosphorus-based antioxidant: the usage of the hindered phenol-based antioxidant is 1: 5 to 2 in mass ratio 1 is preferable and 1: 2 to 1: 1 is more preferable.

  Examples of phosphorus-based antioxidants include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by ADEKA; trade name: Adekastab HP-10), tris (2,4-di-) t-Butylphenyl) phosphite (manufactured by BASF AG; trade name: IRGAFOS 168), and 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa- 3,9-Diphosphaspiro [5.5] undecane (manufactured by ADEKA; trade name: Adekastab PEP-36) and the like are preferable.

  As hindered phenol-based antioxidants, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF; trade name IRGANO01010), and octadecyl-3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by BASF AG; trade name IRGANO01076) and the like are preferable.

The thermal deterioration inhibitor is capable of preventing thermal deterioration of the resin by trapping polymer radicals generated when exposed to high heat under substantially oxygen-free conditions.
As a thermal degradation inhibitor, 2-t-butyl-6- (3'-t-butyl-5'-methyl-hydroxybenzyl) -4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilizer GM), 2,4-di-t-amyl-6- (3 ′, 5′-di-t-amyl-2′-hydroxy-α-methylbenzyl) phenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd .; trade name: Sumilizer GS), etc. preferable.

As a polymer processing aid, polymer particles having a particle diameter of 0.05 to 0.5 μm, which are usually produced by an emulsion polymerization method, are used. Such polymer particles may be single-layer particles consisting of a single composition and single limiting viscosity polymer, or multilayer particles consisting of two or more kinds of polymers differing in composition or limiting viscosity. Good.
In particular, particles of a two-layer structure having a polymer layer having a relatively low intrinsic viscosity in the inner layer and a polymer layer having a relatively high intrinsic viscosity of 5 dl / g or more in the outer layer are preferred.

  The average degree of polymerization of the polymer processing aid is preferably 3,000 to 40,000, more preferably 6,000 to 30,000, and particularly preferably 10,000 to 25,000.

  The composition of the polymer processing aid is preferably a polymer compound comprising 60% by mass or more of methyl methacrylate units and 40% by mass or less of vinyl monomer units copolymerizable therewith.

As a vinyl monomer copolymerizable with methyl methacrylate,
Methacrylates such as ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate;
Acrylic esters such as ethyl acrylate, methyl acrylate, butyl acrylate, and cyclohexyl acrylate
Aromatic vinyl compounds such as styrene, p-methylstyrene and o-methylstyrene;
Maleimide compounds such as N-propyl maleimide, N-cyclohexyl maleimide, and N-o-chlorophenyl maleimide;
Multifunctionality such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, triethylene glycol dimethacrylate, hexanediol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, triethylene glycol diacrylate, allyl methacrylate, and triallylisocyanurate Monomers etc. are mentioned.

As the polymer processing aid, specifically, Metabrene-P series manufactured by Mitsubishi Rayon Co., Ltd. and Paraloid series manufactured by Rohm and Haas Co., Ltd. are preferable.
The polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too low, the improvement effect of the molding processability of the resin sheet for nailing of the present invention tends to be low. If the limiting viscosity is too high, the molding processability of the resin sheet for nailing of the present invention tends to decrease.

  In the present specification, unless otherwise specified, the average degree of polymerization of the polymer processing aid is the degree of polymerization in terms of PMMA measured at 20 ° C. using chloroform as a solvent, using an automatic dilution capillary viscometer (Ubbelohde type). .

  The total amount of additives which can be contained in the resin sheet for nailing of the present invention is preferably 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 4% by mass or less.

(Manufacturing method of resin sheet for nailing)
The resin sheet for nailing of the present invention is manufactured by a known molding method such as an extrusion molding method, a cast molding method, and an injection molding method.
Among the above, extrusion molding is preferred.

The manufacturing method of resin sheet for nailing is
A step (1) of preparing a resin composition (C) by melt-kneading a plurality of types of raw materials containing at least one resin (preferably a methacrylic resin (A)) as a main component and a lubricant (X) ,
It is preferable to have the process (2) of extrusion-molding the resin composition (C).

<Step (1)>
For example, by melt-kneading a main component resin (preferably a methacrylic resin (A)), a lubricant (X), an acrylic rubber (B) if necessary, and an optional component as required, a resin composition ( C) can be manufactured.
In the step (1), a plurality of types of raw materials may be collectively melt-kneaded, or a plurality of types of raw materials may be separately melt-kneaded in a plurality of times.
Melt-kneading can be performed using melt-kneading apparatuses, such as a kneader ruder, an extruder, a mixing roll, and a Banbury mixer, for example.
The kneading temperature is appropriately adjusted in accordance with the melting temperature of the resin component, and is preferably in the range of usually 150 ° C. to 300 ° C.

  The melt flow rate (MFR) determined by measuring the resin composition (C) under conditions of 230 ° C. and 3.8 kg load is preferably 0.1 g / 10 min or more, more preferably 0.2 to 30 g / l. It is 10 minutes, more preferably 0.5 to 20 g / 10 minutes, particularly preferably 1.0 to 10 g / 10 minutes.

  The resin composition (C) can be in the form of pellets or the like as needed in order to enhance the convenience during storage, transportation, or molding.

<Step (2)>
The structure of a resin sheet manufacturing apparatus according to an embodiment of the present invention and a manufacturing method using the same will be described with reference to the drawings.
FIG. 1 is a schematic view of a manufacturing apparatus.

  As shown in FIG. 1, the apparatus 1 for producing a resin sheet includes an extrusion molding means 110 which heats and melts a resin composition 210M (resin composition (C)) as a raw material and extrudes it into a sheet.

In the present embodiment,
The extrusion means 110 is
A raw material feeding portion 111 such as a hopper into which the raw resin composition 210M is charged;
A screw portion 112 which heats, melts and extrudes the resin composition 210M;
It is an extruder with a T-die provided with a T-die 113 including a discharge port 113A for discharging the heat-melted resin composition 210M in a sheet form.

  The temperature of the resin sheet 210 discharged from the T-die 113 is preferably 160 to 270 ° C., more preferably 220 to 260 ° C.

The apparatus 1 for producing a resin sheet is also disposed adjacent to each other with a spacing apart corresponding to the desired thickness of the resin sheet 210, and the sheet material extruded by the T-die-attached extrusion molding means 110 is added It has the cooling roll unit 120 which consists of a plurality of cooling rolls which press and cool.
The cooling roll unit 120 includes at least a first cooling roll 121 and a second cooling roll 122 having a separation portion below the discharge port 113A of the T-die 113.

  The sheet-like material extruded from the T-die 113 is sandwiched between the first cooling roll 121 and the second cooling roll 122, and is pressurized and cooled to form a resin sheet 210. At this point, the resin sheet 210 is not sufficiently cooled and is not completely solidified.

In the illustrated example, the cooling roll unit 120 includes a first cooling roll 121, a second cooling roll 122, a third cooling roll 123, and a fourth cooling roll 124.
The obtained resin sheet 210 held between the first cooling roll 121 and the second cooling roll 122 and pressurized and cooled is separated from the first cooling roll 121 and is separated from the second cooling roll 122. It cools while passing over the surface, is provided between the second cooling roll 122 and the third cooling roll 123, and is pressurized.
The resin sheet 210 is further cooled while passing away from the second cooling roll 122 and passing over the surface of the third cooling roll 123, and provided between the third cooling roll 123 and the fourth cooling roll 124, It is pressurized.
After the resin sheet 210 is further cooled while passing away from the third cooling roll 123 and passing over the surface of the fourth cooling roll 124, the resin sheet 210 leaves the fourth cooling roll 124 and proceeds to the next step. At this time, the resin sheet 210 is not sufficiently cooled and is not completely solidified.

In the present embodiment, the T-die 113 and the cooling roll unit 120 of the extrusion molding means 110 are disposed in the first manufacturing chamber R1.
The environmental temperature in the first production chamber R1 is not particularly adjusted, and is, for example, about 35 to 40 ° C. higher than the normal temperature (20 to 25 ° C.) due to the presence of the heat melting resin.

In the present embodiment, a second manufacturing room R2 is provided adjacent to the first manufacturing room R1.
The environmental temperature in the second manufacturing chamber R2 is preferably adjusted within a temperature range of 20 to 50 ° C. in order to gradually cool the resin sheet 210 obtained by being pressurized and cooled by the cooling roll unit 120. .
The environmental temperature in the second production room R2 can be adjusted using a known air conditioning facility or the like.

The resin sheet manufacturing apparatus 1 also has a protective film bonding means 130 for bonding the protective film 220 on the front and back surfaces of the manufactured resin sheet 210.
The protective film sticking means 130 includes a first protective film roll 131 for supplying the protective film 220 to the surface of the resin sheet 210 and a second protective film roll 132 for supplying the protective film 220 to the back surface of the resin sheet 210. Including.
The protective film sticking means 130 is provided outside the second manufacturing room R2.
Since the resin sheet 210 after being gradually cooled in the second production room R2 is sufficiently cooled and solidified sufficiently, the adhesion process of the protective film 220 particularly needs to control the environmental temperature. Absent.

  The resin sheet manufacturing apparatus 1 also has a pulling means 140 that develops a force of pulling the manufactured resin sheet 210. The take-off means 140 includes a pair of take-up rolls 141 and 142 which are disposed to face each other at the upper and lower sides with a separation part corresponding to the desired thickness of the resin sheet 210 therebetween.

The resin sheet manufacturing apparatus 1 also has a known cutting means (not shown) for cutting the resin sheet 210 having the protective film 220 attached on both sides in a plate shape.
In addition, the structure of the manufacturing apparatus 1 of the resin sheet of this embodiment is only an example, and a design change is possible suitably.

The resin sheet 210 is manufactured as follows using the resin sheet manufacturing apparatus 1 of the present embodiment.
First, the resin composition 210M of the raw material is heated and melted by the extrusion molding means 110 and extruded into a sheet form.
Next, the sheet material extruded by the extrusion molding means 110 is pressurized and cooled by the cooling roll unit 120 to obtain the resin sheet 210.
Next, the obtained resin sheet 210 is gradually cooled in the second production room R2.
Next, the protective film 220 is stuck on both sides of the resin sheet 210 by the protective film sticking means 130.
Next, the resin sheet 210 with the protective film 220 attached on both sides is cut into a plate shape by a known cutting means (not shown).
As described above, the plate-like resin sheet 210 is manufactured.

  In the present embodiment, the entire temperature of the resin sheet 210 is within the range of 120 to 160 ° C. at the time of leaving the cooling roll on the most downstream side of the cooling roll unit 120 (the fourth cooling roll 124 in the example shown in FIG. 1). It is preferable to adjust to

In the present embodiment, when using a methacrylic resin as the transparent resin, the temperature of the entire resin sheet 210 is within the range of 120 to 160 ° C. at the time of leaving the cooling roll most downstream of the cooling roll unit 120. Preferably, the number of cooling rolls used in the cooling roll unit 120 and the temperature of each cooling roll are set.
The number of cooling rolls is preferably 3 to 4.
When a methacrylic resin is used as the transparent resin, the temperature of each cooling roll is, for example, preferably 80 to 100 ° C., more preferably 85 to 95 ° C. for the first cooling roll 121, and the second cooling roll 122 The temperature is preferably 85 to 105 ° C., more preferably 90 to 100 ° C., and the third cooling roll 123 and the fourth cooling roll 124 are preferably 80 to 100 ° C., more preferably 85 to 95 ° C.

  The temperature of the resin sheet 210 on the production line can be measured by a known method, and for example, the surface temperature of the resin sheet 210 can be measured using a non-contact thermometer such as an infrared radiation thermometer. .

In the cooling roll unit 120,
The circumferential speed of the first cooling roll 121 is V1, the circumferential speed of the second cooling roll 122 is V2, the circumferential speed of the third cooling roll 123 is V3, and the circumferential speed of the fourth cooling roll 124 is V4. I assume.
The circumferential speed of the pair of take-up rolls 141 and 142 is assumed to be VX.
In order to smoothly take out the resin sheet 210, VX is usually set equal to or higher than V1 to V4.
The temperature of the resin sheet 210 passing between the pair of take-up rolls 141 and 142 is lower than the temperature of the resin sheet 210 passing through the cooling roll unit 120. In consideration of the thermal contraction amount of the resin sheet 210 of the temperature difference, VX may be set slightly lower than V1 to V4.
For example, it is preferable to adjust the ratio (peripheral velocity ratio VX / V2) of the peripheral velocity VX of the pair of take-up rolls 141 and 142 to the peripheral velocity V2 of the second cooling roller 122 within the range of 0.97 to 1.01. It is more preferable to adjust in the range of 0.99 to 1.01.

  As described above, according to the present invention, a good lubricating effect is obtained, and the frictional heat between the resin sheet and the tool is suppressed to reduce the appearance quality of the machined surface of the resin sheet and the resin fusion to the tool. Thus, it is possible to provide a resin sheet for nailing which can stably suppress loosening or falling of a driven nail even under a temperature environment of 40 ° C. or higher.

  Examples according to the present invention and comparative examples will be described.

Example 1
<Production of Acrylic Three-Layered Structured Particles (BX-1a)>
In a reactor with a reflux condenser, 145 parts by mass of ion exchanged water, 0.45 parts by mass of sodium stearate (SS), 0.08 parts by mass of sodium lauryl sarcosinate (LSS), and sodium carbonate (SC) 0.05 After charging the mass part and stirring and dissolving, 32.9 mass parts of methyl methacrylate (MMA), 2.1 mass parts of methyl acrylate (MA), and allyl methacrylate (ALMA) 0.07 as a crosslinking agent The mass part was charged and the temperature was raised to 80 ° C. while stirring. Next, 1.8 parts by mass of a 2% aqueous solution of potassium persulfate was added, and the temperature was raised to 80 ° C. and held for 60 minutes to obtain a latex.
In the presence of the above latex, 2.2 parts by mass of a 2% aqueous solution of potassium persulfate is charged, 36.99 parts by mass of butyl acrylate (BA), 8.01 parts by mass of styrene (ST), and methacryl as a crosslinking agent A monomer mixture consisting of 0.9 parts by mass of allyl allyl (ALMA) was continuously added over 60 minutes, and was maintained for 30 minutes after the addition was completed.
Next, 1.0 part by mass of a 2% aqueous solution of potassium persulfate is charged in the presence of the above latex, 18.8 parts by mass of methyl methacrylate (MMA), 1.2 parts by mass of methyl acrylate (MA), n-octylmercaptan A monomer mixture consisting of 0.04 parts by mass of (n-OM) was continuously added over 30 minutes, and kept for 60 minutes after the addition was completed.
As described above, from the center side, an acrylic having an average particle diameter of 0.23 μm, which comprises the hard layer (first layer), the soft layer (second layer, rubber layer), and the hard layer (third layer). A latex containing 40% by mass of three-layer structured particles (BX-1a) was obtained.
The monomer composition of each layer of the obtained acrylic three-layer structured particle (BX-1a) and the mass ratio of each layer are as shown in Table 1.

<Production of Raw Material Resin Composition>
Obtained by emulsion-polymerizing 90 parts by mass of MMA and 10 parts by mass of MA for dispersion of the acrylic three-layer structured particle (BX-1a) obtained in Production Example 1, and having an average particle diameter of 0.13 μm A latex of the first methacrylic resin (A-1) having a degree of polymerization of 960 was prepared.
A latex obtained by mixing the acrylic three-layer structured particle (BX-1a) latex obtained in Production Example 1 and the latex of the first methacrylic resin (A-1) in a mass ratio of 67: 33 is coagulated by a known method It filtered, wash | cleaned, dehydrated, and dried, and obtained the 1st methacrylic resin composition (C-1).

Separately, powdery second methacrylic resin (average particle diameter is 0.13 μm, polymerization degree is 1550) obtained by suspension polymerization of 94 parts by mass of MMA and 6 parts by mass of MA A-2) was prepared.
As a lubricant (X), 0.02% by mass of cetanol and 0.1% by mass of monoglyceride stearate are added to the second methacrylic resin (A-2) to form a lubricant-containing methacrylic resin (A) -2L).

  The first methacrylic resin composition (C-1) and the lubricant-added methacrylic resin (A-2L) are melt mixed at a mass ratio of 43:57 to obtain a second methacrylic resin composition ((2) C-2) was obtained. This 2nd methacrylic resin composition (C-2) was used as a raw material resin composition of a resin sheet.

The amount of each lubricant (X) and the total amount of lubricant (X) in the raw resin composition were as shown in Table 2.
Table 2 also shows the melting points (m.p.) of cetanol and monoglyceride stearate used as the lubricant (X).

<Production of resin sheet>
Using the manufacturing apparatus as shown in FIG. 1, the resin sheet of thickness 10 mm was extrusion-molded using the 2nd methacrylic resin composition (C-2) obtained above.
When the cross section of the obtained resin sheet was observed using TEM, the average particle diameter of the acrylic three-layer structured particle (BX-1a) in the sheet was 0.21 μm.
Moreover, the acetone soluble part was removed about one piece of the obtained resin sheet, and it was 23 mass% when the content of the acryl-type three-layer structure particle (BX-1a) in a sheet was measured.

(Comparative Examples 1 and 2)
Production of a raw material resin composition of a resin sheet and production of a resin sheet were carried out in the same manner as in Example 1 except that the addition amount of each lubricant (X) to the second methacrylic resin (A-2) was changed. did.

In Comparative Example 1, 0.005% by mass of Setanol is added as a lubricant (X) to the second methacrylic resin (A-2), and no monoglyceride stearate is added, and a lubricant-containing methacrylic acid for comparison is used. Base resin (A-2M) was obtained.
The first methacrylic resin composition (C-1) obtained in the same manner as in Example 1 and the above-described lubricant-added methacrylic resin (A-2M) are melt mixed at a mass ratio of 43:57, and compared. The raw material resin composition for was obtained.

In Comparative Example 2, as a lubricant (X), 0.02% by mass of setanol is added to the second methacrylic resin (A-2), and 0.6% by mass of monoglyceride stearate is added for comparison. Lubricant-added methacrylic resin (A-2P) was obtained.
The first methacrylic resin composition (C-1) obtained in the same manner as in Example 1 and the above-described lubricant-added methacrylic resin (A-2P) are melt mixed at a mass ratio of 43:57, and compared. The raw material resin composition for was obtained.

  The amount of each lubricant (X) in the raw material resin composition of Comparative Examples 1 and 2 and the total amount of lubricant (X) were as shown in Table 2.

<Evaluation of cutting workability>
Carbide router bit (manufactured by Shibata Tekko Co., Ltd., Basic NC Router machine “NC5001”) with cemented carbide router bit (manufactured by Shibata Tekko Co., Ltd., diameter: 3 mm, blade angle: relief angle 17 degrees, rake angle: 25 degrees, number of teeth) : 1, Material: using cemented carbide steel), drilling of resin sheet while cooling by cutting powder suction method under cutting conditions of rotational speed 17000 rpm, cutting speed 1.5 m / min, cutting length 28 mm A cutting process was performed to evaluate the surface roughness of the machined surface.
The surface roughness was evaluated by arithmetic mean roughness Ra (μm) measured according to JIS B 0601 (2001).
Arithmetic mean roughness Ra is measured under the conditions of measurement magnification 2000, measurement speed 0.5 mm / sec, evaluation length 4 mm, cut-off value 0.8 mm using Kosaka Research Institute Ltd. surf coder "SE700". did.
Moreover, the appearance evaluation of the cutting surface was implemented by visual observation as follows.
When the entire surface of the machined surface had a gloss, it was evaluated as good (+, plus), and the other as poor (-, minus).
Those in which no chipping was observed on the machined surface were evaluated as good (+, plus), and those observed in the evaluation were evaluated as defective (-, minus).
Those in which no resin fusion was observed on the cut surface were evaluated as good (+, plus), and those observed were evaluated as defective (-, minus).

<Evaluation of nail removal properties>
A total of 10 through holes were formed at intervals of 10 mm with a drill of 1.73 mm diameter using a drilling machine for the resin sheet manufactured in each example.
Next, inside each through hole, brass screw nail round point (1.85 mm diameter, length 26.5 mm of part excluding nail head, length 5.5 mm of screw part) by 10 mm depth I typed in.
Next, after heating at 45 ° C. in a suspended state using a hot air oven for 1 hour, the resin sheet was taken out from the hot air oven and sufficiently cooled naturally at room temperature.
Next, using Autograph "AG-2000B" manufactured by Shimadzu Corporation, select any one nail out of a total of 10 nails driven into the resin sheet, and hold the nail head with a chuck. The maximum load (kg) when withdrawn at a speed of 25 mm per minute was measured.
The above measurement was carried out for each of ten nails, and the average value of the maximum load was determined as nailing strength.
Those with a nail removal strength of 50 kgf or more were evaluated as good (+, plus), and those with less than 50 kgf were evaluated as poor (-, minus).

<Evaluation result>
The evaluation results are shown in Table 3.

In Example 1 in which 0.01 to 0.3% by mass of the lubricant (X) is added, the frictional heat between the resin sheet and the tool is suppressed by the lubricating effect to reduce the appearance quality of the machined surface of the resin sheet and the tool It was possible to suppress the resin fusion to the.
The resin sheet obtained in Example 1 in which 0.01 to 0.3% by mass of the lubricant (X) is added has a high nailing strength under a temperature environment of 40 ° C. or more, and under a temperature environment of 40 ° C. or more Nail penetration was stably suppressed.

  In Comparative Example 1 in which the addition amount of the lubricant (X) is less than 0.01% by mass, the lubricating effect is insufficient, and the frictional heat between the resin sheet and the tool can not be sufficiently suppressed. A decrease in the appearance quality of the machined surface and resin fusion to the tool were observed.

  The resin sheet obtained in Comparative Example 2 in which the additive amount of the lubricant (X) is more than 0.3% by mass has a low nailing strength under a temperature environment of 40 ° C. or more, and under a temperature environment of 40 ° C. or more Nail penetration was not stably suppressed.

  The present invention is not limited to the above embodiments and examples, and design changes can be made as appropriate without departing from the spirit of the present invention.

DESCRIPTION OF REFERENCE NUMERALS 1 manufacturing apparatus 110 extrusion molding means 111 raw material feeding portion 112 screw portion 113 T die 113 A discharge port 120 cooling roll unit 121 first cooling roll 122 second cooling roll 123 third cooling roll 124 fourth cooling roll 130 protection Film sticking means 131, 132 Protective film roll 140 Take-off means 141, 142 Take-up roll 210 Resin sheet 210M Resin composition 220 Protective film R1 First production room R2 Second production room

Claims (9)

A fatty acid monoglyceride comprising at least one resin as a main component, a partial ester of a fatty acid having 16 to 22 carbon atoms and glycerin and having a melting point of 45 to 100 ° C., and a carbon number of 12 to 12 having a melting point of 45 to 100 ° C. It comprises a resin composition containing 0.01 to 0.3% by mass of plural kinds of lubricants (X) containing 18 aliphatic alcohols ,
Thickness is 5 mm or more,
Resin sheet for nailing that is used under an environment of 40 ° C or higher. The resin sheet for nailing according to claim 1, wherein the melting points of the plurality of lubricants (X) differ by 5 ° C or more. The resin sheet for nailing according to claim 1 or 2 , wherein the resin is a thermoplastic resin. The resin sheet for nailing according to claim 3 , wherein the resin is a methacrylic resin (A) and / or a carbonate resin. The resin sheet for nailing according to any one of claims 1 to 4 , wherein the resin is a methacrylic resin (A), and the resin composition further contains an acrylic rubber (B). The resin sheet for nailing according to claim 5 , wherein the acrylic rubber (B) contains multilayer structure particles (BX) including at least one rubber layer.   The resin sheet for nailing according to claim 6, wherein a content of multilayer structure particles (BX) in the resin composition is 15% by mass or more. The resin sheet for nailing according to claim 5 , wherein the acrylic rubber (B) contains a block copolymer (BY). A step (1) of preparing a resin composition by melt-kneading a plurality of types of raw materials including at least one type of resin as a main component and a plurality of types of lubricants (X);
And (2) extruding the resin composition.
The manufacturing method of the resin sheet for nailing in any one of Claims 1-8 .

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