JP6317131B2 - Plate-shaped molded body made of methacrylic resin composition - Google Patents

Description

  The present invention relates to a plate-like molded body made of a methacrylic resin composition. More specifically, the present invention is a methacrylic resin composition excellent in mechanical properties, surface smoothness, transparency, etc. and having a small change in haze in a wide temperature range, which is suitable as a molding material for a light guide plate used in a planar light source element. The present invention relates to a plate-like molded body made of a product.

  In general, methacrylic resin is excellent in optical properties such as transparency and weather resistance, so conventionally, display members used for lighting fixtures, signboards, etc., optical members used for display devices, interior members, building members, electronic / electrical members It is used in various applications including medical parts. In these applications, in addition to optical properties and weather resistance, mechanical properties such as flexibility, flex resistance, impact resistance, and flexibility are often required.

  As a method for improving the mechanical properties, a methacrylic resin composition in which various other resins are added to a methacrylic resin has been proposed. For example, a methacrylic resin composition comprising a methacrylic resin and a block copolymer having a methacrylic ester polymer block and an acrylic ester polymer block is known (see Patent Documents 1 and 2).

International Publication No. 2010/055798 International Publication No. 2012/057079

  In general, the refractive index of the resin varies depending on the temperature. The above methacrylic resin composition has the temperature dependence of the refractive index of the methacrylic resin, and other added resins (for example, the methacrylic ester polymer block and the acrylate polymer block in Patent Documents 1 and 2). Since the temperature dependency of the refractive index of the block copolymer) is different, the light transmittance sometimes varies depending on the temperature. For this reason, in applications where transparency is required in a wide temperature range, for example, optical member applications such as a light guide plate used in a liquid crystal display device, problems may occur.

  An object of the present invention is from a methacrylic resin composition which is suitable as a molding material for a light guide plate used for a planar light source element, is excellent in mechanical properties, surface smoothness, transparency and the like and has a small change in haze in a wide temperature range. It is providing the plate-shaped molded object which becomes.

  As a result of intensive studies, the present inventors have completed an invention including the following aspects.

[1]: 10 to 99 parts by mass of a methacrylic resin (A) having a structural unit derived from methyl methacrylate of 80% by mass or more, and 10 to 80% by mass of a methacrylic acid ester polymer block (b1) and an acrylic ester polymer 90 to 1 part by mass of block copolymer (B) having 90 to 20% by mass of block (b2) (however, the total of methacrylic resin (A) and block copolymer (B) is 100 parts by mass) The weight average molecular weight Mw _{(A) of} the methacrylic resin (A), the maximum weight average molecular weight Mw _{(b1) of} the methacrylic ester polymer block _(b1) , and the acrylic ester polymer block (b2). The largest weight average molecular weight Mw _(b2) is composed of a methacrylic resin composition satisfying the following (1) and (2): at least one of the two main surfaces A plate-like molded body having an uneven structure on the side.
(1) 0.5 ≦ Mw _(A) / Mw _(b1) ≦ 2.5
(2) 40000 ≦ Mw _(b2) ≦ 120,000
[2]: The plate-shaped molded product according to [1], wherein the block copolymer (B) has a refractive index of 1.485 to 1.495.
[3]: The acrylic ester polymer block (b2) is 50 to 90% by mass of structural units derived from an alkyl acrylate ester, and 50 to 10% by mass of structural units derived from an aromatic (meth) acrylate ester. The plate-like molded product according to [1] or [2].
[4]: A planar light source element comprising: the plate-shaped molded body according to any one of [1] to [3]; and a light source positioned on an end surface of the plate-shaped molded body.
[5]: The planar light source element according to [4], which is a front light of a display device.
[6]: The planar light source element according to [4], which is a backlight of a display device.

  The plate-shaped molded article of the present invention is excellent in mechanical properties, surface smoothness, transparency, and the like, and has a small change in haze over a wide temperature range. Therefore, it is suitable for various optical applications, particularly a planar light source element.

  The methacrylic resin composition used in the present invention contains a methacrylic resin (A) and a block copolymer (B).

  In the methacrylic resin (A) used in the present invention, the proportion of structural units derived from methyl methacrylate is 80% by mass or more, preferably 90% by mass or more. In the methacrylic resin (A), the proportion of structural units derived from monomers other than methyl methacrylate is 20% by mass or less, preferably 10% by mass or less.

  Examples of the monomer other than methyl methacrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, and t-acrylate. Butyl, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate; phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-acrylate Hydroxyethyl, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate; acrylate esters such as cyclohexyl acrylate, norbornenyl acrylate, isobornyl acrylate; ethyl methacrylate, n-propylene methacrylate , Isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, Pentadecyl methacrylate, dodecyl methacrylate; phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate; cyclohexyl methacrylate, methacryl Methacrylic acid esters other than methyl methacrylate such as norbornenyl acid and isobornyl methacrylate; Unsaturation such as acrylic acid, methacrylic acid, maleic anhydride, maleic acid and itaconic acid Rubonic acid; Olefin such as ethylene, propylene, 1-butene, isobutylene and 1-octene; Conjugated dienes such as butadiene, isoprene and myrcene; Aromatics such as styrene, α-methylstyrene, p-methylstyrene and m-methylstyrene Examples of the vinyl compound include acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl pyridine, vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride.

  The stereoregularity of the methacrylic resin (A) is not particularly limited, and for example, those having stereoregularity such as isotactic, heterotactic and syndiotactic may be used.

The weight average molecular weight Mw _(A) of the methacrylic resin (A) is preferably 30,000 to 180,000, more preferably 40,000 to 150,000, and particularly preferably 50,000 to 130,000. is there. When Mw _(A) is small, the impact resistance and toughness of the plate-like molded product obtained from the resulting methacrylic resin composition tend to be reduced. When Mw _(A) is large, the fluidity of the methacrylic resin composition tends to decrease and the molding processability tends to decrease.

Ratio of weight average molecular weight Mw _(A) and number average molecular weight Mn _(A) of methacrylic resin (A), Mw _(A) / Mn _(A) (hereinafter, ratio of weight average molecular weight to number average molecular weight (weight average molecular weight / The number average molecular weight) may be referred to as “molecular weight distribution.”) Is preferably 1.03 to 2.6, more preferably 1.05 to 2.3, and particularly preferably 1.2 to 2. 0 or less. When the molecular weight distribution is small, the molding processability of the methacrylic resin composition tends to decrease. When the molecular weight distribution is large, the impact resistance of the plate-like molded body obtained from the methacrylic resin composition is lowered and tends to be brittle.
Mw _(A) and Mn _(A) are standard polystyrene equivalent values measured by GPC (gel permeation chromatography).
The molecular weight and molecular weight distribution of the methacrylic resin can be controlled by adjusting the types and amounts of the polymerization initiator and the chain transfer agent.

  The methacrylic resin is obtained by polymerizing a monomer (mixture) containing 80% by mass or more of methyl methacrylate.

  In the present invention, a commercially available product may be used as the methacrylic resin (A). Examples of such commercially available methacrylic resins include “Parapet H1000B” (MFR: 22 g / 10 min (230 ° C., 37.3 N)) and “Parapet GF” (MFR: 15 g / 10 min (230 ° C., 37.3 N). )), “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)), “Parapet HRL” (MFR: 2.0 g / 10 min (230 ° C., 37.3 N)) and “ Parapet G ”(MFR: 8.0 g / 10 min (230 ° C., 37.3 N)) [all trade names, manufactured by Kuraray Co., Ltd.] and the like.

  The block copolymer (B) used in the present invention has a methacrylic acid ester polymer block (b1) and an acrylate polymer block (b2). The block copolymer (B) may have only one methacrylic acid ester polymer block (b1) or a plurality thereof. Moreover, the block copolymer (B) may have only one acrylic ester polymer block (b2) or a plurality thereof.

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

Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methacrylic acid. Amyl acid, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methacrylic acid Examples include 2-hydroxyethyl, 2-methoxyethyl methacrylate, glycidyl methacrylate, and allyl methacrylate. Among these, from the viewpoint of improving transparency and heat resistance, methacrylic acid such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate. Alkyl esters are preferred, and methyl methacrylate is more preferred.
A methacrylic acid ester polymer block (b1) can be formed by polymerizing these methacrylic acid esters alone or in combination of two or more.

  The methacrylic acid ester polymer block (b1) may contain a structural unit derived from a monomer other than the methacrylic acid ester as long as the object and effect of the present invention are not hindered. The proportion of structural units derived from monomers other than methacrylate ester contained in the methacrylate polymer block (b1) is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass. Hereinafter, the range is particularly preferably 2% by mass or less.

  Examples of monomers other than methacrylic acid esters include acrylic acid esters, unsaturated carboxylic acids, aromatic vinyl compounds, olefins, conjugated dienes, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, Examples thereof include vinyl ketone, vinyl chloride, vinylidene chloride, and vinylidene fluoride. A methacrylic acid ester polymer block (b1) can be formed by copolymerizing these monomers other than the methacrylic acid ester alone or in combination of two or more with the above methacrylic acid ester.

  The methacrylic acid ester polymer block (b1) is composed of a polymer having a refractive index in the range of 1.485 to 1.495, and thus the transparency of the methacrylic resin composition or the plate-shaped molded body made of the same. It is preferable from the viewpoint of enhancing.

  The weight average molecular weight of the methacrylic acid ester polymer block (b1) is preferably 5,000 to 150,000, more preferably 8,000 to 120,000, still more preferably 12,000 to 100,000. It is.

  When there are a plurality of methacrylate polymer blocks (b1) in the block copolymer (B), the composition ratio and molecular weight of the structural units constituting each methacrylate polymer block (b1) are the same. May be different or different.

The maximum weight average molecular weight Mw _(b1) of the methacrylic acid ester polymer block (b1) is preferably 12,000 or more and 150,000 or less, more preferably 15,000 or more and 120,000 or less, and still more preferably 20, 000 or more and 100,000 or less. When the block copolymer (B) has only one methacrylate polymer block (b1), the weight average molecular weight of the methacrylate polymer block (b1) is Mw _(b1) . Further, when the block copolymer (B) has a plurality of methacrylate ester polymer blocks (b1), and the plurality of methacrylate ester polymer blocks (b1) have the same weight average molecular weight. Has a weight average molecular weight of Mw _(b1) .

In the methacrylic resin composition used in the present invention, the ratio of the weight average molecular weight Mw _(A) of the methacrylic resin (A ₎ to Mw _(b1) , that is, Mw _(A) / Mw _(b1) is 0.5 or more. It is 5 or less, preferably 0.6 or more and 2.3 or less, more preferably 0.7 or more and 2.2 or less. When Mw _(A) / Mw _(b1) is less than 0.5, the impact resistance of the molded product produced from the methacrylic resin composition tends to be lowered. On the other hand, when Mw _(A) / Mw _(b1) is too large, the surface smoothness and the haze temperature dependence of the plate-like molded body produced from the methacrylic resin composition tend to deteriorate. When Mw _(A) / Mw _(b1) is in the above range, the dispersed particle size in the methacrylic resin (A) of the block copolymer (B) becomes small, so that low haze is exhibited regardless of temperature change. This means that the change in haze is small over a wide temperature range.

  The ratio of the methacrylic ester polymer block (b1) in the block copolymer (B) is preferably 10% by mass or more and 80% by mass or less from the viewpoint of transparency, flexibility, molding processability, and surface smoothness. Preferably they are 10 mass% or more and 70 mass% or less, More preferably, they are 15 mass% or more and 60 mass% or less, Most preferably, they are 20 mass% or more and 55 mass% or less. When the proportion of the methacrylic acid ester polymer block (b1) in the block copolymer (B) is within the above range, the transparency, flexibility, flex resistance of the methacrylic resin composition or a plate-like molded product made thereof, Excellent impact resistance and flexibility. When a plurality of methacrylate ester polymer blocks (b1) are contained in the block copolymer (B), the above ratio is calculated based on the total mass of all methacrylate ester polymer blocks (b1).

  The acrylate polymer block (b2) is mainly composed of a structural unit derived from an acrylate ester. The proportion of structural units derived from the acrylate ester in the acrylate polymer block (b2) is preferably 45% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, and particularly preferably 90% by mass. % Or more.

  Examples of the acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and acrylic. Amyl acid, Isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, acrylic acid Examples include 2-hydroxyethyl, 2-methoxyethyl acrylate, glycidyl acrylate, and allyl acrylate. An acrylic acid ester polymer block (b2) can be formed by polymerizing these acrylic acid esters alone 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 as long as the object and effect of the present invention are not hindered. The proportion of structural units derived from monomers other than the acrylate ester contained in the acrylate polymer block (b2) is preferably 55% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass. Hereinafter, it is particularly preferably 10% by mass or less.

  As monomers other than the acrylic ester, methacrylic ester, unsaturated carboxylic acid, aromatic vinyl compound, olefin, conjugated diene, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl acetate, vinyl pyridine, vinyl ketone, Examples include vinyl chloride, vinylidene chloride, and vinylidene fluoride. The acrylic acid ester polymer block (b2) can be formed by copolymerizing these monomers other than the acrylic acid ester alone or in combination of two or more with the above acrylic acid ester.

The acrylic ester polymer block (b2) may be composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester from the viewpoint of improving the transparency of the methacrylic resin composition or a plate-like molded product made of the same. preferable.
Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and the like. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are preferred.

The (meth) acrylic acid aromatic ester means an acrylic acid aromatic ester or a methacrylic acid aromatic ester, and is formed by ester-bonding a compound containing an aromatic ring to (meth) acrylic acid. Examples of such (meth) acrylic acid aromatic esters include phenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, styryl acrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, styryl methacrylate, and the like. It is done. Of these, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, and benzyl acrylate are preferred.
When the acrylic acid ester polymer block (b2) is composed of an acrylic acid alkyl ester and a (meth) acrylic acid aromatic ester, the acrylic acid ester polymer block (b2) is a structural unit derived from an acrylic acid alkyl ester. It is preferable to contain 50 to 90% by mass and 50 to 10% by mass of structural units derived from (meth) acrylic acid aromatic ester, and 60 to 80% by mass of structural units derived from alkyl acrylate and (meth) acrylic. It is more preferable that 40-20 mass% of structural units derived from an acid aromatic ester are included.

  The acrylic ester polymer block (b2) is composed of a polymer having a refractive index in the range of 1.485 to 1.495, and thus the transparency of the methacrylic resin composition or the plate-like molded body made of the same. It is preferable from the viewpoint of enhancing.

  The weight average molecular weight of the acrylate polymer block (b2) is 5,000 or more and 120,000 or less, preferably 15,000 or more and 110,000 or less, more preferably 40,000 or more and 100,000 or less.

  When there are a plurality of acrylate polymer blocks (b2) in the block copolymer (B), the composition ratio and molecular weight of the structural units constituting each acrylate polymer block (b2) are the same. May be different or different.

The maximum weight average molecular weight Mw _(b2) of the acrylate polymer block (b2) is 40,000 to 120,000, preferably 45,000 to 110,000, more preferably 50,000 to 100. , 000 or less. When Mw _(b2) is small, the impact resistance of a molded product produced from the methacrylic resin composition tends to decrease. On the other hand, when Mw _(b2) is large, the surface smoothness of a molded product produced from the methacrylic resin composition tends to be lowered. When the block copolymer (B) has only one methacrylate polymer block (b2), the weight average molecular weight of the methacrylate polymer block (b2) is Mw _(b2) . Further, when the block copolymer (B) has a plurality of methacrylate ester polymer blocks (b1), and the plurality of methacrylate ester polymer blocks (b1) have the same weight average molecular weight. The weight average molecular weight is Mw _(b2) .

The weight average molecular weight of the methacrylic acid ester polymer block (b1) and the weight average molecular weight of the acrylate polymer block (b2) were sampled during and after the polymerization in the process of producing the block copolymer (B). Is a value calculated from the weight average molecular weight of the intermediate product and the final product (block copolymer (B)) measured by performing Each weight average molecular weight is a standard polystyrene conversion value measured by GPC (gel permeation chromatography).

  The proportion of the acrylate polymer block (b2) in the block copolymer (B) is preferably 20% by mass or more and 90% by mass or less from the viewpoint of transparency, flexibility, molding processability, and surface smoothness. Preferably they are 30 mass% or more and 90 mass% or less, More preferably, they are 40 mass% or more and 85 mass% or less, Most preferably, they are 45 mass% or more and 80 mass% or less. When the ratio of the acrylate polymer block (b2) in the block copolymer (B) is within the above range, the plate-shaped molded article made of the methacrylic resin composition is excellent in impact resistance, flexibility, and the like. When a plurality of acrylic ester polymer blocks (b2) are contained in the block copolymer (B), the above ratio is calculated based on the total mass of all the acrylic ester polymer blocks (b2).

  A block copolymer (B) is not specifically limited by the coupling | bonding form of a methacrylic ester polymer block (b1) and an acrylate ester polymer block (b2). For example, a methacrylic acid ester polymer block (b1) having one end connected to one end of an acrylate polymer block (b2) (diblock copolymer having a (b1)-(b2) structure); methacrylic acid One in which one end of the acrylate polymer block (b2) is connected to each of both ends of the ester polymer block (b1) (triblock copolymer having a structure (b2)-(b1)-(b2)); A triblock copolymer having a (b1)-(b2)-(b1) structure in which one end of a methacrylic acid ester polymer block (b1) is connected to each of both ends of the acrylate polymer block (b2) ) And other methacrylic acid ester polymer blocks (b1) and acrylic acid ester polymer blocks (b2) are connected in series. And the like.

In addition, a block copolymer ([(b1)-(b2)-] _n X structure) in which one terminal of a plurality of block copolymers having a (b1)-(b2) structure is connected to form a radial structure; (B2)-(b1) block copolymer having one end connected to form a radial structure ([(b2)-(b1)-] _n X structure); a plurality of (b1)- (B2)-(b1) block copolymer having one end connected to form a radial structure ([(b1)-(b2)-(b1)-] _n X structure); A block copolymer ([(b2)-(b1)-(b2)-] _n X structure in which one end of a block copolymer having a structure (b2)-(b1)-(b2) is connected to form a radial structure) ) And the like, and block copolymers having a branched structure, etc. Here, X represents a coupling agent residue.
Among these, a diblock copolymer, a triblock copolymer, and a star block copolymer are preferable, and a diblock copolymer having a (b1)-(b2) structure, (b1)-(b2)-(b1 ) Structure triblock copolymer, [(b1)-(b2)-] _n X structure star block copolymer, [(b1)-(b2)-(b1)-] _n X structure star A block copolymer is more preferred.

Further, the block copolymer (B) may have a polymer block (b3) other than the methacrylic ester polymer block (b1) and the acrylate polymer block (b2).
The main structural units constituting the polymer block (b3) are structural units derived from monomers other than methacrylic acid esters and acrylic acid esters. Examples of such monomers include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, α-methylstyrene, p-methylstyrene, m- Aromatic vinyl compounds such as methylstyrene; vinyl acetate, vinyl pyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, ε-caprolactone, valerolactone, etc. .

  In the block copolymer (B), the bonding form of the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3) is not particularly limited. As a bonding form of the block copolymer (B) comprising the methacrylic ester polymer block (b1), the acrylate polymer block (b2) and the polymer block (b3), for example, (b1)-(b2) Examples thereof include a block copolymer having a structure of-(b1)-(b3) and a block copolymer having a structure of (b3)-(b1)-(b2)-(b1)-(b3). When there are a plurality of polymer blocks (b3) in the block copolymer (B), the composition ratio and molecular weight of the structural units constituting each polymer block (b3) may be the same as each other, May be different.

  The block copolymer (B) may have a functional group such as a hydroxyl group, a carboxyl group, an acid anhydride, or an amino group in the molecular chain or at the molecular chain end as necessary.

The weight average molecular weight Mw _(B) of the block copolymer _(B) is preferably from 52,000 to 400,000, more preferably from 60,000 to 300,000.
If the weight average molecular weight of the block copolymer (B) is small, sufficient melt tension cannot be maintained in melt extrusion molding, and it is difficult to obtain a good plate-shaped product, and the resulting plate-shaped product has a breaking strength. The mechanical properties such as On the other hand, when the weight average molecular weight of the block copolymer (B) is large, the viscosity of the molten resin is increased, and the surface of the plate-like molded body obtained by melt extrusion molding is finely textured and unmelted (high There is a tendency that unevenness due to the (molecular weight body) is generated and it is difficult to obtain a good plate-like molded body.

The molecular weight distribution of the block copolymer (B) is preferably 1.0 or more and 2.0 or less, more preferably 1.0 or more and 1.6 or less. When the molecular weight distribution is in such a range, the content of unmelted material that causes generation of scum in the plate-like molded body made of the methacrylic resin composition can be made extremely small.
In addition, a weight average molecular weight and a number average molecular weight are molecular weights of standard polystyrene conversion measured by GPC (gel permeation chromatography).

  The refractive index of the block copolymer (B) is preferably from 1.485 to 1.495, more preferably from 1.487 to 1.493. When the refractive index is within this range, the transparency of the methacrylic resin composition or a plate-like molded product made from the methacrylic resin composition increases. In the present specification, “refractive index” means a value measured at a measurement wavelength of 587.6 nm (d-line) as in the examples described later.

  The manufacturing method of a block copolymer (B) is not specifically limited, The method according to a well-known method is employable. For example, a method of living polymerizing monomers constituting each polymer block is generally used. Examples of such living polymerization methods include anionic polymerization in the presence of mineral acid salts such as alkali metals or alkaline earth metal salts using organic alkali metal compounds as polymerization initiators, and polymerization of organic alkali metal compounds. A method of anionic polymerization in the presence of an organoaluminum compound used as an initiator, a method of polymerization using an organic rare earth metal complex as a polymerization initiator, a method of radical polymerization in the presence of a copper compound using an α-halogenated ester compound as an initiator Etc. In addition, a method of producing a mixture containing the block copolymer (B) used in the present invention by polymerizing monomers constituting each block using a polyvalent radical polymerization initiator or a polyvalent radical chain transfer agent, etc. Also mentioned. Among these methods, in particular, the block copolymer (B) can be obtained with high purity, the molecular weight and the composition ratio can be easily controlled, and it is economical. A method in which anionic polymerization is used in the presence of an organoaluminum compound is preferred.

The methacrylic resin composition used in the present invention contains 10 to 99 parts by weight of methacrylic resin (A) and 90 to 1 parts by weight of block copolymer (B), preferably 15 to 95 parts by weight of methacrylic resin (A) and block. It contains 85 to 5 parts by mass of the copolymer (B), more preferably 20 to 90 parts by mass of the methacrylic resin (A) and 80 to 10 parts by mass of the block copolymer (B).
When the content of the methacrylic resin (A) in the methacrylic resin composition is less than that of the block copolymer (B), fine streaks are formed on the surface of the plate-like molded body obtained by melt extrusion molding using a T die. Concavities and convexities are generated, and there is a tendency that it is difficult to obtain a plate-like molded article having good surface smoothness. On the other hand, when the content of the methacrylic resin (A) is larger than that of the block copolymer (B), the tensile elastic modulus of the plate-shaped molded body made of the methacrylic resin composition tends to increase and the flexibility tends to decrease. .

The methacrylic resin composition used in the present invention may contain various additives as necessary. However, if the content of the additive is too large, appearance defects such as silver may occur in the molded product, so the content is preferably 1% by mass or less.
Additives include heat stabilizers, antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, inorganic fillers, inorganic or organic fibers, mineral oil softeners, polymer processing Auxiliaries, antistatic agents, flame retardants, dyes and pigments, colorants, matting agents, light diffusing agents, impact resistance modifiers, phosphors, adhesives, tackifiers, plasticizers, foaming agents, etc. .

The antioxidant alone has an effect of preventing oxidative deterioration of the resin in the presence of oxygen. Examples thereof include phosphorus antioxidants, hindered phenol antioxidants, and thioether antioxidants. These antioxidants can be used alone or in combination of two or more. Among these, from the viewpoint of preventing the 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. preferable.
In the case where a phosphorus antioxidant and a hindered phenol antioxidant are used in combination, the ratio is not particularly limited, but is preferably a mass ratio of phosphorus antioxidant / hindered phenol antioxidant, preferably 1/5. ˜2 / 1, more preferably ½ to 1/1.

  As the phosphorus-based antioxidant, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (manufactured by Asahi Denka Co., Ltd .; trade name: ADK STAB HP-10), Tris (2,4-dit -Butylphenyl) phosphite (manufactured by Ciba Specialty Chemicals; trade name: IRUGAFOS168).

  As the hindered phenol-based antioxidant, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Ciba Specialty Chemicals; trade name IRGANOX 1010), Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (manufactured by Ciba Specialty Chemicals; trade name IRGANOX1076), 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: ADK STAB PEP-36) and the like.

The thermal degradation inhibitor can prevent thermal degradation of the resin by scavenging polymer radicals generated when exposed to high heat in a substantially oxygen-free state.
As the 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 Sumitizer GS) Can be mentioned.

The ultraviolet absorber is a compound having an ability to absorb ultraviolet rays. The ultraviolet absorber is a compound that is said to have a function of mainly converting light energy into heat energy.
Examples of the ultraviolet absorber include benzophenones, benzotriazoles, triazines, benzoates, salicylates, cyanoacrylates, succinic anilides, malonic esters, formamidines, and the like. These can be used alone or in combination of two or more. Among these, benzotriazoles and anilides are preferable.

As benzotriazoles, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN329), 2 -(2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (manufactured by Ciba Specialty Chemicals; trade name TINUVIN234) and the like.
Examples of the anilides include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant Japan; trade name Sundebore VSU).
Of these ultraviolet absorbers, benzotriazoles are most preferably used from the viewpoint of suppressing resin deterioration due to ultraviolet irradiation.

  The light stabilizer is a compound that is said to have a function of capturing radicals generated mainly by oxidation by light. Suitable light stabilizers include hindered amines such as compounds having a 2,2,6,6-tetraalkylpiperidine skeleton.

  A mold release agent is a compound having a function of facilitating release of a molded product from a mold. Examples of the release agent include higher alcohols such as cetyl alcohol and stearyl alcohol; glycerin higher fatty acid esters such as stearic acid monoglyceride and stearic acid diglyceride. In the present invention, it is preferable to use a higher alcohol and a glycerin fatty acid monoester in combination as a release agent. When higher alcohols and glycerin fatty acid monoester are used in combination, the ratio is not particularly limited, but the mass ratio of higher alcohols / glycerin fatty acid monoester is preferably 2.5 / 1 to 3.5 / 1. Preferably it is 2.8 / 1 to 3.2 / 1.

The polymer processing aid is a compound that exhibits an effect on thickness accuracy and thinning when a methacrylic resin composition is molded. The polymer processing aid is polymer particles having a particle diameter of 0.05 to 0.5 μm, which can be usually produced by an emulsion polymerization method.
The polymer particles may be single layer particles composed of polymers having a single composition ratio and single intrinsic viscosity, or multilayer particles composed of two or more kinds of polymers having different composition ratios or intrinsic viscosities. May be. Among these, particles having a two-layer structure having a polymer layer having a low intrinsic viscosity in the inner layer and a polymer layer having a high intrinsic viscosity of 5 dl / g or more in the outer layer are preferable.

  The polymer processing aid preferably has an intrinsic viscosity of 3 to 6 dl / g. If the intrinsic viscosity is too small, the effect of improving moldability is low. When the intrinsic viscosity is too large, the melt fluidity of the methacrylic resin composition is likely to be lowered.

  An impact modifier may be used in the methacrylic resin composition used in the present invention. Examples of the impact modifier include a core-shell type modifier containing acrylic rubber or diene rubber as a core layer component; a modifier containing a plurality of rubber particles, and the like.

As the organic dye, a compound having a function of converting ultraviolet rays that are harmful to the resin into visible light is preferably used.
Examples of the light diffusing agent and matting agent include glass fine particles, polysiloxane-based crosslinked fine particles, crosslinked polymer fine particles, talc, calcium carbonate, and barium sulfate.
Examples of the phosphor include a fluorescent pigment, a fluorescent dye, a fluorescent white dye, a fluorescent brightener, and a fluorescent bleach.
Mineral oil softeners are used to improve fluidity during molding. Examples thereof include paraffinic oil and naphthenic oil.
Examples of the inorganic filler include calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate. Examples of the fibrous filler include glass fiber and carbon fiber.

  Moreover, the methacrylic resin composition used for this invention can be mixed and used with other polymers other than a methacrylic resin (A) and a block copolymer (B) in the range which does not impair the effect of this invention. Examples of such other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymer, high impact polystyrene, Styrenic resins such as AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin; methyl methacrylate-styrene copolymer; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, polyamide elastomer Polyamides such as: polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyacetal, polyvinylidene fluoride Polyurethanes, modified polyphenylene ether, polyphenylene sulfide, silicone-modified resins; acrylic rubber, silicone rubber; SEPS, SEBS, styrene-based thermoplastic elastomers such as SIS, IR, EPR, and olefin-based rubber such as EPDM and the like.

  The methacrylic resin composition used in the present invention has a melt flow rate of preferably 0.6 g / 10 min or more, more preferably 1 to 20 g / 10 min at 230 ° C. and 37.3 N based on ISO 1173, Preferably it is 1.5-10 g / 10min.

  The method for preparing the methacrylic resin composition used in the present invention is not particularly limited. For example, a method of polymerizing a monomer mixture containing methyl methacrylate in the presence of the block copolymer (B) to produce a methacrylic resin (A), a block copolymer (B) and a methacrylic resin (A) And a method of melt-kneading and the like. Among these, the melt-kneading method is preferable because the process is simple. In the melt-kneading, other polymers and additives may be mixed as necessary, and after mixing the block copolymer (B) with other polymers and additives, the methacrylic resin (A) and The methacrylic resin (A) may be mixed with other polymers and additives and then mixed with the block copolymer (B). The kneading can be performed using, for example, a known mixing apparatus or kneading apparatus such as a kneader ruder, an extruder, a mixing roll, or a Banbury mixer. Of these, a twin screw extruder is preferred. Although the temperature at the time of mixing and kneading | mixing can be suitably adjusted according to the melting temperature etc. of the block copolymer (B) and methacryl resin (A) to be used, Preferably it is 110 to 300 degreeC. The methacrylic resin composition used in the present invention prepared by the method as described above can be used as a molding material in any form such as pellets, granules, and powders.

  Such a methacrylic resin composition according to the present invention is formed by injection molding (including insert method, two-color method, press method, core back method, sandwich method, etc.), compression molding, extrusion molding, vacuum molding, blow molding, The plate-like molded product of the present invention can be obtained by melt-heating molding by a conventionally known method such as inflation molding, calendar molding, melt casting method or the like. Here, the plate-like molded body is a concept including a sheet and a film.

  Examples of the use of the plate-shaped molded article of the present invention include billboard parts such as advertising towers, stand signs, sleeve signs, column signs, and rooftop signs; display parts such as showcases, partition plates, and store displays; fluorescent lamp covers, Lighting parts such as mood lighting covers, lamp shades, light ceilings, light walls, chandeliers; interior parts such as pendants and mirrors; doors, domes, safety window glass, partitions, staircases, balconies, roofs of leisure buildings, etc. Building parts; aircraft windshield, pilot visor, motorcycle, motorboat windshield, bus shading plate, automotive side visor, rear visor, head wing, headlight cover, etc. transportation equipment related parts; acoustic image nameplate, stereo cover, Electronics such as TV protective masks and vending machine display covers Equipment parts; Medical equipment parts such as incubators and X-ray parts; Equipment-related parts such as machine covers, instrument covers, laboratory equipment, rulers, dials, observation windows; light guide plates and films for front lights of display devices, and backlights Optical components such as light guide plates and films, LCD protective plates, Fresnel lenses, lenticular lenses, front panels of various displays, diffusers, reflectors; traffic-related components such as road signs, guide plates, curve mirrors, sound barriers, etc. Surface materials for interiors, surface materials for mobile phones, film members such as marking films; members for household appliances such as canopy materials and control panels for washing machines, top panels for rice cookers; other greenhouses, large tanks, box tanks, Clock panels, bathtubs, sanitary, desk mats, game parts, toys, masks for face protection when welding, etc. It is below.

The plate-like molded product of the present invention is excellent in surface smoothness and mechanical properties, excellent in flexibility, and excellent in optical properties such as light transmittance of short wavelength light. , Optical devices such as printed wiring boards, speakers, microscopes, binoculars, cameras, watches, and other parts related to video, optical recording, optical communication, and information devices. Finders, filters, prisms for cameras, VTRs, projection TVs, etc. , Fresnel lens, protective film for various optical discs (VD, CD, DVD, MD, LD, etc.) substrate, optical switch, optical connector, liquid crystal display, light guide film / sheet for liquid crystal display, flat panel display, guide for flat panel display Optical film / sheet, plasma display, light guide film for plasma display Sheet, light guide film / sheet for electronic paper, retardation film / sheet, polarizing film / sheet, polarizing plate protective film / sheet, wavelength plate, light diffusion film / sheet, prism film / sheet, reflective film / sheet, reflective Prevention film / sheet, viewing angle widening film / sheet, antiglare film / sheet, brightness enhancement film / sheet, display element substrate for liquid crystal and electroluminescence, touch panel, light guide film / sheet for touch panel, various front plates and various modules The present invention can be particularly suitably applied to various optical uses such as a spacer in between.
Specifically, for example, various liquid crystal display elements such as mobile phones, digital information terminals, pagers, navigation, in-vehicle liquid crystal displays, liquid crystal monitors, light control panels, displays for OA devices, displays for AV devices, and electroluminescence displays It can be used for an element or a touch panel. Moreover, from the point which is excellent in a weather resistance, a softness | flexibility, etc., for example, a building interior / exterior member, a curtain wall, a roof member, a roofing material, a window member, a gutter, an exterior, a wall material, a flooring material Further, the present invention can be particularly suitably applied to known building material applications such as construction materials, road construction members, retroreflective films and sheets, agricultural films and sheets, lighting covers, signboards, and translucent sound insulation walls.

Moreover, the plate-shaped molded body of the present invention has a concavo-convex structure formed on at least one of the main surfaces when two opposing surfaces having a large area of the plate-shaped molded body are used as the main surface. And the uneven structure may be formed in both main surfaces. Examples of the concavo-convex structure include grooves, ridges, protrusions, and holes. When the concavo-convex structure is formed on both main surfaces, that is, the front surface and the back surface, the concavo-convex structure on one surface and the other concavo-convex structure may be the same or different.

  The plate-shaped molded product of the present invention is composed of the methacrylic resin composition used in the present invention described above. The plate-shaped molded product includes those having a thickness of 0.005 mm or more and 0.25 mm or less (sometimes referred to as a film) and those having a thickness exceeding 0.25 mm (sometimes referred to as a sheet). The thickness of the plate-shaped molded body of the present invention is preferably 0.025 mm or more and 10 mm or less, more preferably 0.05 mm or more and 5 mm or less from the viewpoint of flexibility and the like.

  The plate-like molded product of the present invention preferably has an average light transmittance at a light wavelength of 400 to 500 nm at a D65 light source obtained by a spectral light transmittance measurement method, a viewing angle of 2 °, a measurement temperature of 25 ° C., and an optical path length of 150 mm. 50% or more. In the plate-shaped molded article of the present invention, the difference between the average light transmittance at a wavelength of 400 to 500 nm and the average light transmittance at 501 to 780 nm is preferably 25% or less, and more preferably 20% or less. Such a plate-like molded body is suitable as an optical member for guiding light from the end face, such as a light guide plate.

You may give an extending | stretching process to the plate-shaped molded object of this invention. By the stretching treatment, it is possible to obtain a plate-like molded body having increased mechanical strength and hardly cracked. The stretching method is not particularly limited, and examples thereof include a simultaneous biaxial stretching method, a sequential biaxial stretching method, a tuber stretching method, and a rolling method. The temperature at the time of stretching is a temperature that is 10 ° C. higher than the glass transition temperature of the methacrylic resin composition used by the lower limit from the viewpoint that a high-strength plate-like molded article can be obtained, and the upper limit is the methacrylic resin composition used by the upper limit. The temperature is 40 ° C. higher than the glass transition temperature of the product.
If the stretching temperature is too low, the plate-like molded product is easily broken during stretching. If the stretching temperature is too high, the effect of the stretching treatment is not sufficiently exhibited, and the strength of the plate-shaped molded body is hardly increased.
Stretching is usually performed at 100 to 5000% / min.
If the stretching speed is low, the strength is hardly increased and the productivity is also lowered. On the other hand, if the stretching speed is high, the molded body may be broken and uniform stretching may be difficult.
It is preferable to perform heat setting after stretching. By heat setting, a plate-like molded body with less heat shrinkage can be obtained. The thickness of the plate-like molded body obtained by stretching is preferably 10 to 200 μm.

The plate-like molded body of the present invention can be laminated with other members by techniques such as fusion, adhesion, coating, printing, and simultaneous injection molding. For example, hard coat materials, antireflection materials, antifungal materials; organic compounds or compositions such as liquid crystals, cyclic olefin ring-opening polymers or hydrogenated products thereof, addition polymerization type cyclic olefin polymers, aliphatic olefins Examples thereof include organic polymers or compositions such as resins, acrylic polymers, polycarbonate resins, and liquid crystal polymers; inorganic substances or compositions such as soda glass and quartz glass. In order to laminate with other members, a known primer may be applied to the surface, or corona discharge treatment, plasma treatment, or the like may be performed.
In the injection molding simultaneous bonding method, the plate-shaped molded body of the present invention is inserted between male and female molds for injection molding, and a molten thermoplastic resin is injected into the mold from one surface of the plate-shaped molded body, At the same time as forming an injection molded body, the plate-shaped molded body is bonded to the molded body.

The plate-like molded body to be inserted into the mold may be a flat one as it is, or may be a preform formed by vacuum forming, pressure forming or the like and shaped into an uneven shape.
The preforming of the plate-shaped molded body may be performed by a separate molding machine, or may be preformed in a mold of an injection molding machine used for the simultaneous injection molding method. The latter method, that is, a method of pre-molding a plate-shaped molded body and then injecting a molten resin on one side thereof is called an insert molding method.

  The planar light source element of this invention is equipped with the plate-shaped molded object of this invention, and the light source located in the end surface of this plate-shaped molded object. Examples of the light source include an LED and a cold cathode tube. The planar light source element can be used as a backlight or a front light of a display device.

The light guide plate, which is one of the planar light source elements of the present invention, is an element for guiding light so that light entering the end face of the plate is reflected from the back of the plate and exits from the front of the plate. . Irregularities for reflecting light are provided on at least one of the front surface and the back surface of the light guide plate. Further, on the front surface of the light guide plate, a prism or an arc-shaped line-shaped convex portion for increasing the front luminance or deflecting the emission direction is provided as necessary.
The unevenness for reflecting light can be formed by a known method such as fusion, adhesion, coating, printing, injection molding, or processing with laser light. The unevenness is designed to have an optimal structure based on factors such as the size, thickness, thickness of the light guide plate, and the distance from the end surface of the light guide plate to the light source, etc. Is done. Examples of the uneven shape include a perfect circle or elliptical dot pattern, a line pattern such as a rectangle or a V-groove, a hemispherical lens-shaped unevenness, a wrinkle pattern, and the like. The unevenness formed in one light guide plate may be a repeated pattern of the same shape and the same size, a pattern formed by combining different shapes, or a repeated pattern of the same shape and different sizes. May be. The size of the convex portion or the concave portion constituting the unevenness can be, for example, a width of 1 to 600 μm, a length of 2 to 1200 μm, and a height or depth of 1 to 500 μm. Moreover, the distance between the center points of adjacent concave portions or convex portions is preferably 2 to 10,000 μm. The size and interval of the convex portions or the concave portions can be selected according to the required light guiding performance, productivity, and the capability of the manufacturing apparatus. In general, if the concave or convex portions are too large or the interval is too wide, the intensity of the light emitted from the front surface will be uneven, or the intensity of the light emitted from the front surface will be weakened, resulting in poor display quality. There is a tendency to decrease. Conversely, by reducing the size of the recesses or projections or reducing the interval, spots can be reduced. However, since high accuracy is required for the formation of projections and depressions, the productivity is lowered and the cost is reduced. There is a tendency to increase.

  The light guide plate is used as a backlight or a front light for a liquid crystal display or the like. In the backlight, a light reflection sheet can be installed on the back side of the light guide plate, and a light diffusion sheet, a prism sheet, or the like can be installed on the front side of the light guide plate.

When the planar light source element of the present invention is used as a backlight, a white reflector may be provided on the front surface or the back surface.
A white reflective material can be normally installed by printing (for example, screen printing etc.). The size, shape, arrangement, and spacing of the white reflective material are designed to have an optimal structure based on factors such as the size and thickness of the light guide plate and the distance from the light guide plate end surface to the light source. One width or length of the white reflector is preferably 500 μm to 5000 μm, and the distance between the center points of the white reflector is preferably 1000 to 5000 μm. The size and interval of the white reflective material can be selected according to the required light guide performance, productivity, and capability of the manufacturing apparatus. In general, if one of the white reflectors is too large or the interval is too wide, the intensity of light emitted from the front will be uneven, or the intensity of light emitted from the front will be weakened, resulting in poor display quality. There is a tendency to decrease. Conversely, by reducing the size of one of the white reflectors or by reducing the interval, spots can be reduced, but high accuracy is required for printing, which reduces productivity and costs. There is a tendency to increase.

When the planar light source element of the present invention is used as a front light, a white reflective material is not provided on the front surface or the back surface unlike a backlight. This is because the front light sees the display through the light guide plate, so that the reflective material gets in the way when the display is viewed.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by a following example. In addition, the present invention includes all aspects that are obtained by arbitrarily combining the above-described items representing technical characteristics such as characteristic values, forms, manufacturing methods, and uses.

  The measurement of physical property values in Reference Examples and Production Examples was performed by the following method.

[Weight average molecular weight (Mw) and molecular weight distribution]
The weight average molecular weight (Mw) and molecular weight distribution during and after the polymerization of the block copolymer (B) and the methacrylic resin (A) were determined by GPC (gel permeation chromatography) in terms of polystyrene.
-Equipment: GPC equipment "HLC-8020" manufactured by Tosoh Corporation
Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series. Eluent: Tetrahydrofuran Eluent flow rate: 1.0 ml / min Column temperature: 40 ° C.
・ Detection method: Differential refractive index (RI)

[Composition ratio of each polymer block]
The composition ratio of each polymer block was determined by ¹ H-NMR ( ¹ H-nuclear magnetic resonance) measurement.
・ Device: JEOL Nuclear Magnetic Resonance Device “JNM-LA400”
・ Deuterated solvent: Deuterated chloroform

[Refractive index of block copolymer (B)]
A sheet having a size of 3 cm × 3 cm and a thickness of 3 mm was produced by press molding, and the refractive index was measured at 23 ° C. at a measurement wavelength of 587.6 nm (d-line) using “KPR-200”. .

[Haze of injection molded products]
A plate-like molded product having a size of 50 mm × 50 mm and a thickness of 3 mm was obtained at a resin temperature of 240 ° C. and a mold temperature of 55 ° C. with an injection molding machine, and the haze was measured at 23 ° C. in accordance with JIS K7105.

[Bending elastic modulus of injection molded products]
The flexural modulus was measured in accordance with ISO178 from an injection molded product molded at a resin temperature of 240 ° C. and a mold temperature of 55 ° C. by an injection molding machine.

[Impact resistance of injection-molded products (Charpy impact strength)]
Based on ISO1799-1eU, the Charpy impact strength without notch was measured from an injection molded product molded at a resin temperature of 240 ° C. and a mold temperature of 55 ° C. by an injection molding machine.

[Surface smoothness of film]
The film was extruded with a cylinder and T-die temperature of 240 ° C. and a lip gap of 0.5 mm using a T-die film forming machine (model FS-5) manufactured by Optical Control System, thereby obtaining a film having a thickness of 0.1 mm. The surface state of the obtained film having a thickness of 0.1 mm was visually observed, and the result was evaluated according to the following criteria.
◯: There are no irregular streak-like or textured irregularities on the surface, and the appearance quality is excellent.
(Triangle | delta): The surface has a streak-like or irregular uneven | corrugated uneven | corrugated surface, and an external appearance quality is a little inferior.
X: The surface has irregular streak-like and grainy irregularities, and the appearance quality is inferior.

[Sheet windability]
Extruded at a cylinder and T-die temperature of 240 ° C. and a lip gap of 1.0 mm with an optical control system film-forming machine (model FS-5) to extrude a 0.5 mm thick plate-like molded body (sheet), This sheet was wound up on a roll having a core diameter of 50 mmφ. The state at the time of winding was observed, and the result was evaluated according to the following criteria.
○: The sheet can be wound up without breaking.
X: The sheet is broken and cannot be wound.

[Temperature dependence of haze of plate-like molded product]
A 50 mm × 50 mm test piece was cut out from a 0.5 mm thick plate-like molded body molded by the above method, and the haze was measured at 23 ° C. according to JIS K7136 with a direct reading haze meter (manufactured by Nippon Denshoku). did. This measured value was defined as a haze value at 23 ° C.
The test piece was then left in a 60 ° C. incubator for 30 minutes. The test piece was taken out from the thermostat, and immediately, the haze was measured by a direct reading haze meter (manufactured by Nippon Denshoku) in accordance with JIS K7136. This measured value was defined as a haze value at 60 ° C.
The temperature dependency was expressed by the difference between the haze value at 60 ° C. and the haze value at 23 ° C. The smaller the value, the smaller the temperature dependency.

  In the reference examples shown below, the compounds used were dried and purified by a conventional method and degassed with nitrogen. The compound was transferred and supplied in a nitrogen atmosphere.

Reference Example 1 [Synthesis of Block Copolymer (B-1)]
Into a three-necked flask purged with nitrogen and purged with nitrogen, 735 g of dry toluene, 0.4 g of hexamethyltriethylenetetramine, and isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum at room temperature 39.4 g of a toluene solution containing 20 mmol was added, and 1.17 mmol of sec-butyllithium was further added. To this, 35.0 g of methyl methacrylate was added and reacted at room temperature for 1 hour. The polymer contained in the reaction solution was sampled and the weight average molecular weight (hereinafter referred to as Mw _(b1-1) ) was measured and found to be 40,000. The methyl methacrylate polymer is further block copolymerized with an acrylate ester, whereby the methyl methacrylate is converted into a methacrylate polymer block (b1) (hereinafter referred to as “methyl methacrylate polymer block (b1-1)”). Called).

Next, the reaction solution was brought to −25 ° C., and a mixed solution of 49.0 g of n-butyl acrylate and 21.0 g of benzyl acrylate was added dropwise over 0.5 hours. Immediately after the dropping, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured, and it was 120,000. Since the weight average molecular weight of the methyl methacrylate polymer block (b1-1) was 40,000, the weight of the acrylate polymer block (b2) composed of a copolymer of n-butyl acrylate and benzyl acrylate. The average molecular weight (Mw _(b2) ) was determined to be 80,000.

Subsequently, 35.0 g of methyl methacrylate was added, the reaction solution was returned to room temperature, and stirred for 8 hours, whereby the second methacrylate polymer block (b1) (hereinafter, “methyl methacrylate polymer block (b1 -2) "). Thereafter, 4 g of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol to obtain a block copolymer (B) (hereinafter referred to as “block copolymer”) which is a triblock copolymer. B-1) ") was precipitated, filtered, and isolated by drying at 80 ° C. and 1 torr (about 133 Pa) for 12 hours. The obtained block copolymer (B-1) had a weight average molecular weight Mw _(B) of 160,000. Since the weight average molecular weight of the diblock copolymer was 120,000, the weight average molecular weight (referred to as Mw _(b1-2) ) of the methyl methacrylate polymer block (b1-2) was 40,000. Were determined. The weight average molecular weight of methyl methacrylate polymer block _(b1-1) Mw (b1-1), since the weight average molecular weight Mw _(b1-2) are both 40,000 methyl methacrylate polymer block (b1-2) , Mw _(b1) is 40,000.
The obtained block copolymer (B-1) contains 70% by mass of structural units derived from n-butyl acrylate and a structural unit derived from benzyl acrylate in the acrylate polymer block (b2). It had 30 mass%. It is shown in Table 1 together with other analysis results.
In Table 1, the structural unit derived from methyl methacrylate is “MMA”, the structural unit derived from n-butyl acrylate is “BA”, and the structural unit derived from benzyl acrylate is “BzA”. It is written using.

Reference Examples 2 to 6 [Synthesis of Block Copolymers (B-2) to (B-6)]
Block co-polymerization was carried out in the same manner as in Reference Example 1, except that the amounts of hexamethyltriethylenetetramine, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) aluminum, and sec-butyllithium were changed. A union (B) (respectively referred to as block copolymers (B-2) to (B-6)) was synthesized. Table 1 shows the analysis results of the obtained block copolymers (B-2) to (B-6).

Reference Example 7 [Synthesis of Methacrylic Resin (A-1)]
Polymerization initiator (2,2′-azobis (2-methylpropionitrile), hydrogen abstraction capacity: 1%, half-life for 1 hour, in a monomer mixture consisting of 95 parts by weight of methyl methacrylate and 5 parts by weight of methyl acrylate Temperature: 83 ° C., 0.1 part by mass and a chain transfer agent (0.77 part by mass of n-octyl mercaptan were added and dissolved to obtain a raw material liquid.
100 parts by mass of ion-exchanged water, 0.03 parts by mass of sodium sulfate, and 0.46 parts by mass of the suspension / dispersant were mixed to obtain a mixed solution. In a pressure-resistant polymerization tank, 420 parts by mass of the mixed liquid and 210 parts by mass of the raw material liquid were charged, and the polymerization reaction was started at a temperature of 70 ° C. while stirring in a nitrogen atmosphere. After 3 hours from the start of the polymerization reaction, the temperature was raised to 90 ° C. and stirring was continued for 1 hour to obtain a liquid in which the bead copolymer was dispersed. Although some polymer adhered to the wall of the polymerization tank or the stirring blade, there was no foaming and the polymerization reaction proceeded smoothly.
The obtained copolymer dispersion is washed with an appropriate amount of ion-exchanged water, and the bead-shaped copolymer is taken out with a bucket-type centrifuge and dried with a hot air dryer at 80 ° C. for 12 hours. (A) (hereinafter referred to as “methacrylic resin (A-1)”) was obtained.
The resulting methacrylic resin (A-1) had a weight average molecular weight Mw _(A) of 30,000 and a molecular weight distribution of 1.8.

Reference Example 8 [Synthesis of methacrylic resin (A-2)]
_A methacrylic resin (A-2) having a Mw _{(A) of} 55,000 and a molecular weight distribution of 1.8 was obtained in the same manner as in Reference Example 7 except that the amount of the chain transfer agent was changed to 0.45 parts by mass.

Reference Example 9
A methacrylic resin (A-3) having an Mw _(A) of 90,000 and a molecular weight distribution of 1.8 was obtained in the same manner as in Reference Example 7 except that the amount of the chain transfer agent was changed to 0.26 parts by mass. .

Reference Example 10
A methacrylic resin (A-4) having an Mw _(A) of 130,000 and a molecular weight distribution of 1.8 was obtained in the same manner as in Reference Example 7 except that the amount of the chain transfer agent was changed to 0.16 parts by mass. .

Production Example 1
40 parts by mass of the block copolymer (B-1) and 60 parts by mass of the methacrylic resin (A-3) were melt-kneaded at 230 ° C. by a twin screw extruder. Then, the pellet of the methacrylic resin composition was manufactured by extruding and cut | disconnecting.
Using this pellet, haze, flexural modulus, Charpy impact strength, surface smoothness, winding property, and temperature dependence of haze were evaluated according to the above test methods. The results are shown in Table 2.
Production Examples 2 to 10
Pellets were produced in the same manner as in Production Example 1 except that the formulation shown in Table 1 was followed.
Using these pellets, physical properties were measured in the same manner as in Production Example 1. The results are shown in Table 2 and Table 3. In Production Example 10, in place of the block copolymer (B), Kuraray Co., Ltd. cross-linked rubber particle blended resin “Parapet GR-100” was used.

Example 1
The methacrylic resin composition pellets obtained in Production Example 1 were extruded from a die having a width of 350 mm at an extrusion temperature of 250 ° C. and a discharge rate of 60 kg / h using a 65 mmΦ vent type single screw extruder, and a pair of metals at 45 ° C. The film was nipped with a mirror roll and taken out at 10 m / min to form a film having a thickness of 250 μm.
Next, the film was cut into a 150 mm × 200 mm rectangle with the direction parallel to the extrusion flow direction as the long side. Furthermore, using the vacuum press molding machine, the cut film was set between a pair of flat plate molds heated to 135 ° C., and pressure-molded at a pressure of 0.95 MPa for 900 seconds. A plurality of recesses having a depth of 2 μm and a diameter of 5 μm are provided on one surface of the flat plate mold, and the distance between the center points of the recesses is 50 μm in the short side direction and the long side direction of the cut film. Evenly spaced.
The surface of the other flat plate mold is a mirror surface.
By the pressing step, a film was obtained in which convex portions having a height of 2 μm and a diameter of 5 μm were provided on one surface at equal intervals of 50 μm in length and width.

  Next, a white LED was installed as an end light source at 30 mm intervals facing the short side of the film to produce a front light. The front light was placed 10 mm away from the newspaper surface in parallel, and the surface having the convex portion on the surface was placed facing the paper surface. The newspaper surface was visually observed and evaluated through the front light. As shown in Table 4, the paper surface was satisfactorily observed with the end light source turned off in the bright room. Furthermore, the paper surface was satisfactorily observed with the end light source turned on in a dark room.

Example 2
The methacrylic resin composition pellets obtained in Production Example 2 were extruded from a die having a width of 350 mm at a extrusion temperature of 250 ° C. at a discharge rate of 60 kg / h using a 65 mmΦ vent type single screw extruder, and a pair of 45 ° C. And a film having a thickness of 250 μm was formed.
A plurality of recesses having a depth of 2 μm and a diameter of 5 μm are provided on one surface of the metal roll, and the distance between the center points of the recesses is a uniform interval of 50 μm in the rotation direction and the width direction of the metal roll. . The surface of the other metal roll is a mirror surface.
By the extrusion manufacturing process, a film was obtained in which convex portions having a height of 2 μm and a diameter of 5 μm were provided on one surface at equal intervals of 50 μm in length and width.
Next, a front light was produced in the same manner as in Example 1, and visually observed and evaluated. As a result, as shown in Table 4, the paper surface was observed well in each of the bright room and the dark room.

Example 3
The methacrylic resin composition pellets obtained in Production Example 3 were molded using an injection molding machine at a cylinder temperature of 180 ° C. to 220 ° C. and a mold temperature of 60 ° C., and were rectangular having a length of 190 mm and a width of 240 mm and a thickness of 500 μm. A film was formed.
A plurality of recesses having a depth of 2 μm and a diameter of 5 μm are provided on one surface of the mold, and the distance between the center points of the recesses is equal to 50 μm in the short side direction and the long side direction of the film. is there.
The surface of the other flat plate mold is a mirror surface.
The lateral end and longitudinal end of the film obtained in the injection molding process are cut into a rectangular shape of 150 mm × 200 mm, and convex portions having a height of 2 μm and a diameter of 5 μm are formed on one surface at equal intervals of 50 μm in length and width. The provided film was obtained.
Next, a front light was produced in the same manner as in Example 1, and visually observed and evaluated. As a result, as shown in Table 4, the paper surface was observed well in each of the bright room and the dark room.

Comparative Example 1
Using the methacrylic resin composition pellets obtained in Production Example 4, in the same manner as in Example 2, a thickness in which convex portions having a height of 2 μm and a diameter of 5 μm were provided at equal intervals of 50 μm in length and breadth on one surface A film of 250 μm was obtained. Further, a front light was manufactured in the same manner as in Example 1 and evaluated by visual observation. As a result, as shown in Table 4, the front light was cloudy in each of the bright room and the dark room, and the paper surface looked whitish and the contrast was poor.

Comparative Example 2
Using the methacrylic resin composition pellets obtained in Production Example 5, in the same manner as in Example 2, a thickness in which convex portions having a height of 2 μm and a diameter of 5 μm were provided at equal intervals of 50 μm in length and width on one surface A film of 250 μm was obtained. Further, a front light was manufactured in the same manner as in Example 1 and evaluated by visual observation. As a result, as shown in Table 4, streaky appearance defects were conspicuous on the surface of the front light in the bright room.

Comparative Example 3
Using the methacrylic resin composition pellets obtained in Production Example 6, in the same manner as in Example 2, a thickness in which convex portions having a height of 2 μm and a diameter of 5 μm were provided at equal intervals of 50 μm in length and width on one surface A film of 250 μm was obtained. Further, a front light was manufactured in the same manner as in Example 1 and evaluated by visual observation. As a result, as shown in Table 4, streaky appearance defects were conspicuous on the surface of the front light in the bright room.

Comparative Example 4
Using the methacrylic resin composition pellets obtained in Production Example 7, in the same manner as in Example 2, a thickness in which convex portions having a height of 2 μm and a diameter of 5 μm were provided at equal intervals of 50 μm in length and breadth on one surface A film of 250 μm was obtained. Further, a front light was manufactured in the same manner as in Example 1 and evaluated by visual observation. As a result, as shown in Table 4, streaky appearance defects were conspicuous on the surface of the front light in the bright room, and the paper surface looked whitish in the dark room because the front light was cloudy, and the contrast was poor.

Comparative Example 5
Using the methacrylic resin composition pellets obtained in Production Example 10, in the same manner as in Example 2, a thickness in which convex portions having a height of 2 μm and a diameter of 5 μm were provided at equal intervals of 50 μm in length and width on one surface A film of 250 μm was obtained. Further, a front light was manufactured in the same manner as in Example 1 and evaluated by visual observation. As a result, as shown in Table 4, the front light was cloudy in each of the bright room and the dark room, and the paper surface looked whitish and the contrast was poor.

Comparative Example 6
Using a methacrylic resin “Parapet EH” (MFR: 1.3 g / 10 min (230 ° C., 37.3 N)) manufactured by Kuraray Co., Ltd., which does not contain a block copolymer, A film having a thickness of 250 μm was produced in which convex portions having a height of 2 μm and a diameter of 5 μm were provided on the surface at equal intervals of 50 μm in length and width. However, when the film was taken up, it was broken and could not be taken up.

From these results, the weight average molecular weight Mw _{(A) of} the methacrylic resin (A) is 0.5 to 2.5 with respect to the maximum weight average molecular weight Mw _{(b1) of the} methacrylic ester polymer block (b1). A methacrylic resin in the following range and a block copolymer (B) having a maximum weight average molecular weight Mw _{(b2) in} the acrylic acid ester polymer block (b2) in the range of 40000 to 120,000 are 10 / It can be seen that the methacrylic resin composition blended at a mass ratio of 90 to 99/1 is excellent in mechanical properties, surface smoothness, transparency and the like, and the change in haze is small in the temperature range of 23 to 60 ° C. Moreover, it turns out that it is suitable as a light guide as an example, when a plate-shaped molded object is produced from the said methacryl resin and a concavo-convex structure is formed.
That is, the plate-shaped molded body of the present invention is suitable for various optical uses, particularly for planar light source elements.

Claims (6)

Methacrylic resins (A) 6 0 to 99 parts by weight having a structural unit derived from methyl methacrylate or 80 wt%, and methacrylic acid ester polymer block (b1) 10 to 80 wt% and acrylic acid ester polymer block (b2 ) consists of a 90-20 wt%, and (b1) - (tri-block structure der Ru block copolymer b1) (B) 4 0 to 1 parts by weight (however, a methacrylic resin (a - (b2)) A total of 100 parts by mass with the block copolymer (B),
Weight average molecular weight Mw _{(A) of} the methacrylic resin ( _A) ,
The maximum weight average molecular weight Mw of the methacrylic acid ester polymer block _(b1) (b1), and the maximum weight average molecular weight Mw of the acrylic acid ester polymer block _(b2) (b2) are,
A plate-like molded body comprising a methacrylic resin composition satisfying the following (1) and (2) and having an uneven structure formed on at least one of two main surfaces.
(1) 0.5 ≦ Mw _(A) / Mw _(b1) ≦ 2.5
(2) 40000 ≦ Mw _(b2) ≦ 120,000   The plate-shaped molded product according to claim 1, wherein the block copolymer (B) has a refractive index of 1.485 to 1.495.   The said acrylate polymer block (b2) contains 50-90 mass% of structural units derived from alkyl acrylate ester and 50-10 mass% of structural units derived from (meth) acrylic acid aromatic ester. 3. The plate-like molded product according to 1 or 2.   A planar light source element comprising: the plate-shaped molded body according to any one of claims 1 to 3; and a light source positioned on an end surface of the plate-shaped molded body.   The planar light source element according to claim 4, which is a front light of a display device.   The planar light source element according to claim 4, which is a backlight of a display device.