JP2010189520A - Cavity-including resin molded article and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cavity-including resin molded article having large reflectivity and strong piercing strength, and to provide a method for producing the same. <P>SOLUTION: The cavity-including resin molded article comprises a molded polymer article containing a crystalline polymer and a crystal nucleating agent, and includes a cavity inside thereof, and crystallinity of the crystalline polymer contained in the cavity-including resin molded article is ≥10 and <50%. It is preferable that the crystal nucleating agent is an organic crystal nucleating agent and the content of the crystal nucleating agent to the crystalline polymer is ≥0.01 and <10 mass%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a void-containing resin molded body and a method for producing the same.

  In recent years, light reflecting films have been used in various fields such as members for liquid crystal display devices such as personal computers, projection screens, planar light source members, and illumination members. For example, in a liquid crystal display device, it is desired to increase the area of the display device and improve the display performance. One solution is to improve the performance of the backlight unit and supply as much light as possible to the liquid crystal unit. For this purpose, the light reflectance of the light reflecting film is increased as much as possible. There was a need.

  Conventionally, a metal plate or the like has been used as the light reflector. However, there is a problem that the weight per unit area is large, which adversely affects weight reduction and current leaks through the metal plate. In order to solve these problems, attempts have been made to produce resin-made light reflecting films. In order to produce a resin-made light reflecting film, it is necessary to manufacture a film having a roughened surface or a film having a structure that causes light scattering reflection inside the film.

As the light reflecting film, for example, a film made of a crystalline polyester resin and satisfying physical properties required for an LCD backlight has been proposed (for example, see Patent Document 1).
However, the light reflecting film described in Patent Document 1 has a problem that the puncture strength is small and stretching such as Roll to Roll stretching is difficult.

Japanese Patent Laid-Open No. 10-45930

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a void-containing resin molded article having a high reflectivity and a high piercing strength and a method for producing the same.

Means for solving the above problems are as follows. That is,
<1> A void-containing resin molded article comprising a polymer molded article containing a crystalline polymer and a crystal nucleating agent, and containing voids therein, wherein the crystallinity of the crystalline polymer in the void-containing resin molded article is 10% The void-containing resin molded product characterized by being less than 50%.
<2> The void-containing resin molded product according to <1>, wherein the crystal nucleating agent is an organic crystalline nucleating agent.
<3> The void-containing resin molded product according to any one of <1> to <2>, wherein the content of the crystal nucleating agent with respect to the crystalline polymer is 0.01% by mass or more and less than 10% by mass.
<4> The void-containing resin molded product according to any one of <1> to <3>, wherein the crystalline polymer includes at least one of a crystalline polyester resin and a crystalline polyamide resin.
<5> The void-containing resin molded product according to any one of <1> to <4>, wherein the crystalline polyester resin includes at least one of a polyethylene terephthalate resin and a polyethylene naphthalate resin.
<6> The cavity-containing layer according to any one of <1> to <5>, wherein the thickness of the cavity-free layer that does not contain the cavity is 1 μm or more, and the thickness of the cavity-containing layer that contains the cavity is 8 μm or more. It is a resin molding.
<7> A method for producing a void-containing resin molded body for producing the void-containing resin molded body according to any one of <1> to <6>, wherein the stretching step includes stretching the polymer molded body at least uniaxially. The stretching temperature in the stretching step is Tg (° C.) when the stretching temperature is T (° C.), the glass transition temperature of the crystalline polymer is Tg (° C.), and the melting point of the crystalline polymer is Tm (° C.). It is a manufacturing method of the cavity containing resin molding characterized by satisfy | filling (degreeC) <T (degreeC) <(Tm-50) (degreeC).

  ADVANTAGE OF THE INVENTION According to this invention, the said various problems in the past can be solved, the said objective can be achieved, and the cavity containing resin molded object with a large reflectance and a large piercing intensity | strength and its manufacturing method can be provided.

Drawing 1 is a figure showing an example of a manufacturing method of a void content resin fabrication object of the present invention, and is a flow figure of a biaxially stretched film manufacturing device. FIG. 2A is a diagram for specifically explaining the aspect ratio, and is a perspective view of the void-containing resin molded body. FIG. 2B is a diagram for specifically explaining the aspect ratio, and is a cross-sectional view taken along the line A-A ′ of the void-containing resin molded body in FIG. 2A. FIG. 2C is a diagram for specifically explaining the aspect ratio, and is a B-B ′ sectional view of the void-containing resin molded body in FIG. 2A. FIG. 2D is a cross-sectional view taken along the line A-A ′ in FIG. 2A for explaining a method of measuring the distance from the film surface of the ten cavities located closest to the film surface.

(Method for producing void-containing resin molded body and void-containing resin molded body)
The void-containing resin molded product of the present invention can be suitably produced by the production method of the present invention. Hereinafter, the manufacturing method of the void containing resin molding of this invention and the void containing resin molding manufactured by this method are demonstrated.
The method for producing a void-containing resin molded body of the present invention includes at least a stretching step, and further includes other steps such as a film forming step as necessary.

[Stretching process]
The stretching step is a step of stretching a polymer molded body containing a crystalline polymer and a crystal nucleating agent at least uniaxially. The stretching step develops cavities.

<Polymer molded product>
The polymer molded body includes a crystalline polymer and a crystal nucleating agent, and includes other components as necessary.
There is no restriction | limiting in particular as a shape of the said polymer molded object, According to the objective, it can select suitably, For example, a film form, a sheet form, etc. are mentioned.

-Crystalline polymer-
Generally, polymers are classified into polymers having crystallinity (crystalline polymers) and amorphous (amorphous) polymers, but even polymers having crystallinity are not 100% crystalline, It includes a crystalline region in which long chain molecules are regularly arranged and an amorphous region that is not regularly arranged.
Therefore, as the crystalline polymer in the polymer molded body of the present invention, at least the crystalline region may be included in the molecular structure, and the crystalline region and the amorphous region may be mixed.

  There is no restriction | limiting in particular as said crystalline polymer, According to the objective, it can select suitably, For example, high density polyethylene, polyolefin (for example, polypropylene, polyethylene, etc.), polyamides (PA) (for example, nylon) -6, nylon-11, polymetaxylylene adipamide (nylon MXD6), etc.), polyacetals (POM), polyesters (eg, PET, PEN, PTT, PBT, PPT, PHT, PBN, PES, PBS, etc.) ), Syndiotactic polystyrene (SPS), polyphenylene sulfides (PPS), polyether ether ketones (PEEK), liquid crystal polymers (LCP), fluororesins, and the like. Among these, polyesters, polyamides, syndiotactic polystyrene (SPS), and liquid crystal polymers (LCP) are preferable from the viewpoint of mechanical strength and production, and polyesters and polyamides are more preferable.

The melt viscosity of the crystalline polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 Pa · s to 700 Pa · s, more preferably 70 Pa · s to 500 Pa · s, and more preferably 80 Pa · s. s to 300 Pa · s is particularly preferable. When the melt viscosity is 50 Pa · s to 700 Pa · s, the shape of the melt film discharged from the die head during melt film formation is stable, and this is preferable because uniform film formation is facilitated. Further, when the melt viscosity is 50 Pa · s to 700 Pa · s, the viscosity at the time of melt film formation becomes appropriate and the extrusion becomes easy, or the melt film at the time of film formation is leveled to reduce unevenness. This is preferable.
Here, the melt viscosity can be measured by a plate type rheometer or a capillary rheometer.

There is no restriction | limiting in particular as MFR (melt flow rate) of the said crystalline polymer, Although it can select suitably according to the objective, 0.1 (g / 10min)-100 (g / 10min) are preferable, 0 0.5 (g / 10 min) to 60 (g / 10 min) is more preferable, and 1 (g / 10 min) to 35 (g / 10 min) is particularly preferable. When the MFR is 1 (g / 10 min) to 35 (g / 10 min), the strength of the formed film is increased, and this is preferable in that the film can be efficiently stretched.
Here, the MFR can be measured by, for example, a semi-auto melt indexer 2A (manufactured by Toyo Seiki Co., Ltd.).

There is no restriction | limiting in particular as melting | fusing point (Tm) of the said crystalline polymer, Although it can select suitably according to the objective, 40 to 350 degreeC is preferable, 100 to 300 degreeC is more preferable, 100 to 260 degreeC is preferable. ° C is particularly preferred. The melting point is preferably 40 ° C. to 350 ° C. in that it is easy to keep the shape in the temperature range expected for normal use, and even without using special techniques required for processing at high temperatures, It is preferable at the point which can form a uniform film.
Here, the melting point can be measured by a differential thermal analyzer (DSC).

--- Polyester resin--
There is no restriction | limiting in particular as said polyester, According to the objective, it can select suitably, For example, aromatic polyester, aliphatic polyester, etc. are mentioned.
There is no restriction | limiting in particular as said aromatic polyester, Although it can select suitably according to the objective, PET, PTT, and PEN are preferable and PET and PEN are more preferable.
The aliphatic polyester is not particularly limited and may be appropriately selected depending on the intended purpose. PES (polyethylene succinate), PBS (polybutylene succinate), and polylactic acid are preferable, and PBS (polybutylene succinate) ), Polylactic acid is more preferred.
The polyesters (hereinafter sometimes referred to as “polyester resin”) mean a general term for polymer compounds having an ester bond as the main bond chain. Therefore, as the polyester resin suitable as the crystalline polymer, the exemplified PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PTT (polytrimethylene terephthalate), PBT (polybutylene terephthalate), PPT (polypenta). Methylene terephthalate), PHT (polyhexamethylene terephthalate), PBN (polybutylene naphthalate), PES (polyethylene succinate), PBS (polybutylene succinate), polylactic acid as well as dicarboxylic acid component and diol component All polymer compounds obtained by the condensation reaction are included.

  The dicarboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, oxycarboxylic acids, and polyfunctional acids. Among them, aromatic dicarboxylic acids are preferable.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, naphthalenedicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium sulfoisophthalic acid. Acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are preferable, and terephthalic acid, diphenyldicarboxylic acid, and naphthalenedicarboxylic acid are more preferable.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, eicoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, maleic acid, and fumaric acid. Examples of the alicyclic dicarboxylic acid include cyclohexane dicarboxylic acid. Examples of the oxycarboxylic acid include p-oxybenzoic acid. Examples of the polyfunctional acid include trimellitic acid and pyromellitic acid. Among the aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, succinic acid, adipic acid, and cyclohexanedicarboxylic acid are preferable, and succinic acid and adipic acid are more preferable.

  The diol component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diols, alicyclic diols, aromatic diols, diethylene glycol, and polyalkylene glycols. Group diols are preferred.

  Examples of the aliphatic diol include ethylene glycol, propane diol, butane diol, pentane diol, hexane diol, neopentyl glycol, and triethylene glycol. Among them, propane diol, butane diol, pentane diol, and hexane diol are exemplified. Particularly preferred. Examples of the alicyclic diol include cyclohexanedimethanol. Examples of the aromatic diol include bisphenol A and bisphenol S.

  There is no restriction | limiting in particular as melt viscosity of the said polyester resin, Although it can select suitably according to the objective, 50 Pa.s-700 Pa.s are preferable, 70 Pa.s-500 Pa.s are more preferable, 80 Pa.s ˜300 Pa · s is particularly preferred. When the melt viscosity is higher, voids are more likely to occur during stretching, but when the melt viscosity is 50 Pa · s to 700 Pa · s, extrusion becomes easier during film formation, and the resin flow stabilizes and stays. This is preferable in that it becomes difficult and the quality is stabilized. In addition, the melt viscosity of 50 Pa · s to 700 Pa · s is preferable in that the drawing tension is appropriately maintained at the time of drawing, and the film is easily drawn uniformly and is not easily broken. Further, when the melt viscosity is 50 Pa · s to 700 Pa · s, the shape of the molten film discharged from the die head at the time of film formation can be easily maintained, and it can be stably molded or the product is hardly damaged. It is preferable in terms of improving physical properties.

There is no restriction | limiting in particular as intrinsic viscosity (IV) of the said polyester resin, Although it can select suitably according to the objective, 0.4-1.2 are preferable, 0.6-1.0 are more preferable, 0.7 to 0.9 is particularly preferable. When the IV is larger, voids are more likely to be generated during stretching. However, when the IV is 0.4 to 1.2, extrusion is easier during film formation, and the resin flow is stable and retention is less likely to occur. It is preferable in that the quality is stabilized. Furthermore, when the IV is 0.4 to 1.2, the stretching tension is appropriately maintained at the time of stretching, and therefore, it is easy to stretch uniformly and it is preferable in that a load is not easily applied to the apparatus. In addition, when the IV is 0.4 to 1.2, it is preferable in that the product is hardly damaged and the physical properties are increased.
Here, the IV can be measured by an Ubbelohde viscometer.

  There is no restriction | limiting in particular as melting | fusing point of the said polyester resin, Although it can select suitably according to the objective, From viewpoints, such as heat resistance and film forming property, 150 to 300 degreeC is preferable, and 160 to 270 degreeC is preferable. More preferred.

--- Polyamide resin--
The polyamides (hereinafter sometimes referred to as “polyamide resins”) mean polymers obtained by bonding a large number of monomers by amide bonds. Examples of the polyamide resin suitable as the crystalline polymer include nylon and aramid resin. Of these, nylon is preferable.
---- Polyamides ---
There is no restriction | limiting in particular as said polyamides, According to the objective, it can select suitably, For example, polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide ( Nylon 66), polyhexamethylene sebamide (nylon 6/10), polyhexamethylene dodecamide (nylon 6/12), polyundecane adipamide (nylon 11/6), polyundecanamide (nylon 11) , Polydodecanamide (nylon 12), polytrimethylhexamethylene terephthalamide, polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalate / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclohexyl) methane dodecamide (Nylon ACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylenehexa Hydroterephthalamide (nylon 11T (H)), and the like. Among them, nylon 6, nylon 11, nylon 12, nylon 6/10, nylon 6/12, nylon 11/6, and polymetaxylylene adipamide (nylon MXD6) are preferable. Nylon 6, nylon 11, polymetaxylylene adipa Mid (Nylon MXD6) is more preferred.

  There is no restriction | limiting in particular as melt viscosity of the said polyamide resin, Although it can select suitably according to the objective, 50 Pa.s-700 Pa.s are preferable, 70 Pa.s-500 Pa.s are more preferable, 80 Pa.s ˜300 Pa · s is particularly preferred. When the melt viscosity is higher, voids are more likely to occur during stretching, but when the melt viscosity is 50 Pa · s to 700 Pa · s, extrusion becomes easier during film formation, and the resin flow stabilizes and stays. This is preferable in that it becomes difficult and the quality is stabilized. In addition, the melt viscosity of 50 Pa · s to 700 Pa · s is preferable in that the drawing tension is appropriately maintained at the time of drawing, and the film is easily drawn uniformly and is not easily broken. Further, when the melt viscosity is 50 Pa · s to 700 Pa · s, the shape of the molten film discharged from the die head at the time of film formation can be easily maintained, and it can be stably molded or the product is hardly damaged. It is preferable in terms of improving physical properties.

  There is no restriction | limiting in particular as MFR (melt flow rate) of the said polyamide resin, Although it can select suitably according to the objective, 0.1 (g / 10min)-100 (g / 10min) are preferable, and 0.1. 5 (g / 10 min) to 60 (g / 10 min) is more preferable, and 1 (g / 10 min) to 20 (g / 10 min) is particularly preferable. When the MFR is larger, voids are more likely to be exhibited during stretching. However, when the MFR is 0.1 (g / 10 min) to 100 (g / 10 min), it is easy to extrude during film formation, or the flow of resin. Is preferable in that it is difficult to cause stagnation and the quality is stable. Further, when the MFR is 0.5 (g / 10 min) to 60 (g / 10 min), the stretching tension is appropriately maintained at the time of stretching. It is preferable in terms of difficulty. In addition, when the MFR is 1 (g / 10 min) to 20 (g / 10 min), the product is less likely to be damaged, which is preferable in terms of enhancing physical properties.

There is no restriction | limiting in particular as melting | fusing point of the said amide resin, Although it can select suitably according to the objective, From viewpoints, such as heat resistance and film forming property, 150 to 300 degreeC is preferable, and 160 to 270 degreeC is preferable. More preferred.
The number average molecular weight of the amide resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 12,000 to 40,000, more preferably 18,000 to 40,000, More preferably, it is 500-30,000.
When the number average molecular weight is less than 12,000, the mechanical strength may be insufficient when processed into a film or the like, and when it exceeds 40,000, polymerization may be difficult.

―Crystal nucleating agent―
The crystal nucleating agent is not particularly limited and can be appropriately selected depending on the purpose. For example, metal compounds containing a single oxide or a composite oxide, metal salts of low molecular organic compounds containing a carboxyl group, Metal salts of polymer organic compounds containing carboxyl groups, other polymer organic compounds, phosphoric acid and its metal salts, phosphorous acid and its metal salts, sorbitol derivatives, quaternary ammonium compounds, thioglycolic anhydride and its metal salts , P-toluenesulfonic acid and metal salts thereof, dibasic acid bis (benzoic acid hydrazide) compounds, isocyanurate compounds, and compounds having a barbituric acid structure. The crystal nucleating agent may include one or more of those described above.

The crystal nucleating agent may be either an inorganic substance or an organic substance, but the reflectance decreases due to irregular reflection of light caused by the inorganic substance, the yellowing of the resin triggered by irradiation with ultraviolet rays, etc., and the inorganic substance ( Organic crystal nucleating agents such as organic compounds and organic metals are preferable in terms of contamination due to dropping off during the process of particles).
The metal compounds containing the single oxide or composite oxide are not particularly limited and can be appropriately selected according to the purpose. For example, calcium carbonate, synthetic silicate, silicate, silica, zinc white, High-site clay, kaolin, basic magnesium carbonate, mica, talc, quartz powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, boron nitride, etc. Is mentioned.

  The low molecular weight organic compound containing a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, octylic acid, toluic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid , Stearic acid, behenic acid, serotic acid, montanic acid, mellic acid, benzoic acid, p-tert-butylbenzoic acid, terephthalic acid, terephthalic acid monomethyl ester, isophthalic acid, isophthalic acid monomethyl ester, camphoric acid, citronellic acid, hinoki Acid, abietic acid, rosin acid, hydrogenated rosin acid, and the like.

  There is no restriction | limiting in particular as a high molecular organic compound containing the said carboxyl group, According to the objective, it can select suitably, For example, the carboxyl group containing polyethylene obtained by oxidation of polyethylene, the carboxyl group containing obtained by oxidation of polypropylene Polypropylene, olefins (for example, ethylene, propylene, butene-1) and acrylic acid (or methacrylic acid) copolymer, styrene and acrylic acid (or methacrylic acid) copolymer, olefins and anhydrous And a copolymer of maleic acid and a copolymer of styrene and maleic anhydride.

  There is no restriction | limiting in particular as said other high molecular organic compound, According to the objective, it can select suitably, For example, 3,3-dimethylbutene-1, 3-methylbutene-1, 3-methylpentene-1, 3-position branched α-olefins having 5 or more carbon atoms such as 3-methylhexene-1, 3,5,5-trimethylhexene-1; polymers of vinylcycloalkanes such as vinylcyclopentane, vinylcyclohexane, vinylnorbornane; polyethylene Polyalkylene glycols such as glycol and polypropylene glycol; polyglycolic acid; cellulose; cellulose ester; cellulose ether; polyvinyl alcohol; chitin; chitosan; aliphatic polyamide compounds such as nylon 6, nylon 66, nylon 610, nylon 612; And resorcin Wholly aromatic polyester powder as a constituent unit, polyhydroxyalkanoates; and the like.

  There is no restriction | limiting in particular as said phosphoric acid and its metal salt, According to the objective, it can select suitably, For example, diphenyl phosphate, phosphoric acid bis (4-tert- butylphenyl) sodium, methylene phosphate (2 , 4-tert-butylphenyl) sodium, and the like.

  There is no restriction | limiting in particular as said phosphorous acid and its metal salt, According to the objective, it can select suitably, For example, phosphorous acid diphenyl etc. are mentioned.

  There is no restriction | limiting in particular as said sorbitol derivative, According to the objective, it can select suitably, For example, bis (p-methyl benzylidene) sorbitol, bis (p-ethyl benzylidene) sorbitol, etc. are mentioned.

  The quaternary ammonium compound is not particularly limited and may be appropriately selected depending on the intended purpose. Tetraethylammonium chloride, tetran-propylammonium chloride, tetran-butylammonium chloride, tetraethylammonium bromide, tetran-propyl Examples thereof include ammonium bromide, tetra n-butylammonium bromide, tetraethylammonium silicate, tetra n-butylammonium silicate, and the like.

  There is no restriction | limiting in particular as said dibasic acid bis (benzoic acid hydrazide) compound, According to the objective, it can select suitably, For example, what is represented with the following general formula (I) is mentioned.

  There is no restriction | limiting in particular as said isocyanurate compound, According to the objective, it can select suitably, For example, what is represented with the following general formula (II) is mentioned.

  There is no restriction | limiting in particular as a compound which has the said barbituric acid structure, According to the objective, it can select suitably, For example, what is represented by following formula (1)-(7) is mentioned.

(In the formula (1), independently R ^1, R ² and R ³ are each a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Represents a carboxylic acid derivative of 2 to 20), or represents a combination of these groups, and L represents an oxygen atom or a sulfur atom)

(In the formula (2), R ¹ , R ² , R ³ and L represent the same as those in the general formula (1), and R ⁵ and R ⁶ are each independently a hydrogen atom, carbon number 1 An alkyl group which may have 10 to 10 branches or substituents, an alkoxy group which may have 1 to 10 carbon atoms branches or substituents, and a substituent which has 3 to 30 carbon atoms A good cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (3), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and M represents a hydrogen atom or a valence of 1 P is 1, q is 0, and when M is a valence 2 metal atom, q is 0 or an integer of 1, p is 2-q, M Is a valence 3 metal atom, q is an integer from 0 to 2, p is 3-q, M is a valence 4 metal atom, That in the case, q is an integer of 0 to 3, p is 4-q)

(In the formula (4), R ¹ , R ² , R ³ , L, M, p and q are the same as those in the general formula (3), and R ⁵ and R ⁶ are each independently a hydrogen atom, An alkyl group that may have a branch or substituent having 1 to 10 carbon atoms, an alkoxy group that may have a branch or substituent having 1 to 10 carbon atoms, or a substituent that has 3 to 30 carbon atoms. A cyclic group which may have or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

(In the formula (5), R ¹ , R ² , R ³ , R ⁵ and L represent the same as those in the general formula (4)).

(In the formula (6), and each of R ^1, R ² and R ³ independently represents a hydrogen atom, an optionally branched alkyl group having or substituent having 1 to 10 carbon atoms, 1 to 10 carbon atoms An alkoxy group which may have a branch or a substituent, a cyclic group which may have a substituent having 3 to 30 carbon atoms, or —NH—R ⁴ (R ⁴ is the same as R ¹ , or a carbon atom Or a combination of these groups, L represents an oxygen atom or a sulfur atom, M represents a hydrogen atom or a metal atom, and n represents an integer of 1 to 4. To express)

(In the formula (7), R ¹ , R ² , R ³ , L, M and n are the same as those in the general formula (6), and R ⁵ and R ⁶ are each independently a hydrogen atom or a carbon atom. An alkyl group that may have a branch or substituent of 1 to 10, an alkoxy group that may have a branch or substituent of 1 to 10 carbon atoms, or a substituent of 3 to 30 carbon atoms A cyclic group or —NH—R ⁴ (R ⁴ represents the same as R ¹ or a carboxylic acid derivative having 2 to 20 carbon atoms) or a combination of these groups)

  Among the crystal nucleating agents, for example, mica, talc, stearic acid, benzoic acid, terephthalic acid, camphoric acid, abietic acid, rosin acid, hydrogenated rosin acid, olefins (for example, ethylene, propylene, butene-1) and Copolymer with acrylic acid (or methacrylic acid), nylon 6, nylon 66, nylon 610, nylon 612, wholly aromatic polyester fine powder mainly composed of terephthalic acid and resorcin, bis (p-methylbenzylidene) ) Sorbitol, bis (p-ethylbenzylidene) sorbitol, dibasic acid bis (benzoic acid hydrazide) compound, isocyanurate compound, compound having barbituric acid structure is preferred, dibasic acid bis (benzoic acid hydrazide) compound, isocyanurate compound A compound having a barbituric acid structure Ri preferred.

-Content of crystal nucleating agent-
The addition amount of the crystal nucleating agent is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 0.01% by mass or more and less than 10% by mass with respect to the crystalline polymer. More preferably, the content is 0.1% by mass or more and 5% by mass or less. When the amount is less than 0.01% by mass with respect to the crystalline polymer, it may be difficult to obtain a predetermined effect. When 10% by mass or more is blended, an effect corresponding to the blending amount can be expected. In addition to being impractical, it can be uneconomical.

--- Confirmation of presence of crystal nucleating agent ---
A crystalline polymer (for example, polyester resin) containing the crystal nucleating agent is dissolved in, for example, chloroform, hexafluoroisopropanol, etc., a poor solvent for the polyester resin is added, the supernatant solution is concentrated, and the solvent is again made into an appropriate solvent. By dissolving and performing spectroscopic methods such as H-NMR, mass spectrometry, analysis by liquid chromatography, and the like, the type and amount of the crystal nucleating agent can be measured.

-Other ingredients-
The other component is not particularly limited as long as it does not contribute to the development of the cavity, and can be appropriately selected depending on the purpose.

  Examples of the component that does not contribute to the development of the cavity include a heat stabilizer, an antioxidant, an organic lubricant, a nucleating agent, a dye, a pigment, a dispersant, a coupling agent, and a fluorescent brightening agent. Whether or not the other component contributes to the development of the cavity can be determined by whether or not a component other than the crystalline polymer (for example, each component described later) is detected in the cavity or at the interface portion of the cavity.

There is no restriction | limiting in particular as said antioxidant, According to the objective, it can select suitably, For example, well-known hindered phenols etc. are mentioned. Examples of the hindered phenols include antioxidants commercially available under trade names such as Irganox 1010, Similarizer BHT, and Similarizer GA-80.
Further, the antioxidant can be used as a primary antioxidant and further combined with a secondary antioxidant. Examples of the secondary antioxidant include antioxidants commercially available under trade names such as Sumilizer TPL-R, Sumilizer TPM, Sumilizer TP-D, and the like.

  The fluorescent whitening agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, commercially available products with names such as Ubitech, OB-1, TBO, Keicoal, Kayalite, Leukopua, EGM, etc. Can be used. In addition, the said fluorescent whitening agent may be used individually by 1 type, and may use 2 or more types together. By adding the fluorescent whitening agent in this way, it is possible to give a brighter and more bluish whiteness and to have a high-class feeling.

<Extension>
In the stretching, the polymer molded body is stretched at least uniaxially. And by the said extending process, while a polymer molded object is extended | stretched, the cavity orientated along the extending | stretching direction of the 1st axis | shaft is formed in the inside, and a cavity containing resin molded object is obtained.

  The reason why the cavity is formed by stretching is that the crystalline polymer constituting the polymer molded body forms a minute crystal region or a minute region having regularity at a certain level of molecules, and at the time of stretching. It is considered that cavities are formed by peeling and stretching in such a manner that the resin between phases including crystals or microstructure regions that are difficult to stretch is torn off.

  The stretching method is not particularly limited as long as the effects of the present invention are not impaired, and examples thereof include uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching. It is preferable that longitudinal stretching is performed along the direction in which the molded body flows.

In general, in the longitudinal stretching, the number of longitudinal stretching stages and the stretching speed can be adjusted by the combination of rolls and the speed difference between the rolls.
The number of stages of the longitudinal stretching is not particularly limited as long as it is one or more, and can be appropriately selected according to the purpose.
In addition, the stretching conditions (for example, the stretching speed and the stretching temperature) in the second and subsequent stages may be the same as or different from the first stage.

-Stretching speed-
There is no restriction | limiting in particular as the extending | stretching speed | rate of the said longitudinal stretch, Although it can select suitably according to the objective, 10 mm / min-36,000 mm / min are preferable, and 800 mm / min-24,000 mm / min are more preferable. 1,200 mm / min to 12,000 mm / min is particularly preferable. When the stretching speed is 10 mm / min or more, it is preferable in that sufficient necking can be easily expressed. Further, when the stretching speed is 36,000 mm / min or less, uniform stretching is facilitated, the resin is not easily broken, and the cost is reduced without requiring a large stretching apparatus for high-speed stretching. It is preferable in that it can be performed. Therefore, when the stretching speed is 10 mm / min to 36,000 mm / min, sufficient necking is easily developed, uniform stretching is facilitated, the resin is not easily broken, and high speed stretching is intended. This is preferable in that the cost can be reduced without requiring a large stretching apparatus.

  More specifically, the stretching speed in the case of one-stage stretching is preferably 1,000 mm / min to 36,000 mm / min, more preferably 1,100 mm / min to 24,000 mm / min, and 1,200 mm / min. Min to 12,000 mm / min is particularly preferable.

  In the case of two-stage stretching, it is preferable that the first-stage stretching is a preliminary stretching whose main purpose is to develop necking. The stretching speed of the preliminary stretching is preferably 10 mm / min to 300 mm / min, more preferably 40 mm / min to 220 mm / min, and particularly preferably 70 mm / min to 150 mm / min.

  In the two-stage stretching, it is preferable that the second-stage stretching speed after the necking is expressed by the preliminary stretching (first-stage stretching) is changed from the preliminary stretching speed. The stretching speed of the second stage after causing necking by the preliminary stretching is preferably 600 mm / min to 36,000 mm / min, more preferably 800 mm / min to 24,000 mm / min, and 1,200 mm. / Min to 15,000 mm / min are particularly preferable.

There is no restriction | limiting in particular as a measuring method of the said extending | stretching speed, It can select suitably from well-known methods, For example, it can measure with the following method.
In the case of the batch type, the movement speed when the clamp holding the end of the polymer molded body moves in the stretching direction, that is, the movement distance of the clamp / the time (mm / min) required for the movement of the clamp. The stretching speed is used. The stretching speed defined in the present embodiment is the stretching speed in the batch type unless otherwise specified.

  Further, when the polymer molded body is stretched due to a difference in the surface speed of the nip roll when the polymer molded body passes through two pairs (or more) of nip rolls (generally referred to as “Roll to Roll stretching”). In the case, the gripping position of the polymer molded body is fixed by a nip roll and does not move. Therefore, in the case of the above Roll to Roll stretching, the stretch ratio is the stretched ratio / the time required for stretching (% / min). The nip roll corresponds to the roll 15a in FIG.

  The stretching speed in the batch method and the stretching speed in the Roll-to-Roll stretching are the length before stretching (mm) and the length after stretching (mm) of the polymer molded body in any stretching method. If they are measured, they can be converted into each other. Table 1 shows an example in which the stretching speed in the batch method is converted into the stretching speed in Roll to Roll stretching.

--Extension temperature--
As the stretching temperature, when the stretching temperature is T (° C.), the glass transition temperature of the crystalline polymer is Tg (° C.), and the melting point of the crystalline polymer is Tm (° C.), Tg (° C.) <T (° C. ) <(Tm-50) (° C.) As long as the stretching temperature T (° C.) is in the range indicated, there is no particular limitation, and it can be appropriately selected according to the purpose.
When the stretching temperature is a stretching temperature T (° C.) in a range represented by Tg (° C.) <T (° C.) <(Tm−50) (° C.), Roll to Roll stretching becomes possible.

  Here, the stretching temperature T (° C.) can be measured with a non-contact thermometer. The glass transition temperature Tg (° C.) can be measured by a differential thermal analyzer (DSC).

In the stretching step, lateral stretching may or may not be performed as long as it does not hinder the appearance of cavities. In the case of lateral stretching, the film may be relaxed or heat-treated using a lateral stretching process.
Further, the stretched void-containing resin molded body may be further subjected to treatment such as heat shrinkage by applying heat or applying tension for the purpose of shape stabilization.

The method for producing the polymer molded body is not particularly limited and can be appropriately selected depending on the purpose. For example, when the crystalline polymer is a polyester resin or a polyolefin resin, it is preferably used by a melt film forming method. Can be manufactured.
Moreover, the polymer molded body may be produced independently of the stretching step or continuously.

Drawing 1 is a figure showing an example of a manufacturing method of a void content resin fabrication object of the present invention, and is a flow figure of a biaxially stretched film manufacturing device. The biaxially stretched film manufacturing apparatus shown in FIG. 1 is a film manufacturing apparatus that performs Roll to Roll stretching.
As shown in FIG. 1, a raw material resin (polymer composition) 11 is melted in an extruder 12 (a twin screw extruder or a single screw extruder is used depending on the raw material shape and production scale). After being kneaded, the T-die 13 is discharged into a soft plate shape (film or sheet shape).
Next, the discharged film or sheet F is cooled and solidified by the casting drum 14 to form a film. The formed film or sheet F (corresponding to “polymer molded body”) is sent to the longitudinal stretching machine 15.
And the film or sheet | seat F formed into a film is again heated within the longitudinal stretch machine 15, and is stretched | stretched longitudinally between the rolls 15a from which speed differs. By this longitudinal stretching, a cavity is formed in the film or sheet F along the stretching direction. Then, the film or sheet F in which the cavity is formed is gripped at both ends by the left and right clips 16a of the transverse stretching machine 16, and is stretched laterally while being sent to the winder side (not shown). The resin molded body 1 is obtained. In addition, in the said process, you may use the film or sheet | seat F which performed only the longitudinal stretch as the cavity containing resin molded object 1 without using for the horizontal stretcher 16. FIG.

<Cavity-containing resin molding>
The void-containing resin molded body of the present invention can be obtained by the above-described method for producing a void-containing resin molded body.
The void-containing resin molded body is composed of the polymer molded body, and the crystallinity of the crystalline polymer in the void-containing resin molded body is 10% or more and less than 50%.
There is no restriction | limiting in particular as a shape of the said void containing resin molding, According to the objective, it can select suitably, For example, a film form, a sheet form, a fiber form etc. are mentioned.

-Crystallinity of crystalline polymer-
The degree of crystallinity of the crystalline polymer indicates the proportion of the crystalline region in the partially crystallized crystalline polymer.
The crystallinity of the crystalline polymer is not particularly limited as long as it is 10% or more and less than 50%, and can be appropriately selected according to the purpose, but is preferably 12% to 50%, preferably 15% to 50%. % Is more preferable, and 15% to 45% is particularly preferable. When the crystallinity of the crystalline polymer is less than 10%, voids are not sufficiently developed, and the reflectance may be lowered. When the crystallinity is 50% or more, the film may be broken during stretching. is there.
The crystallinity of the crystalline polymer can be appropriately changed by adjusting the content of the crystal nucleating agent and the heat treatment process.
-Analytical measurement method for crystallinity of crystalline polymer-
The crystallinity of the crystalline polymer can be determined by an X-ray diffraction method, a density method, or a thermal (DSC) measurement method.
In the present invention, the crystallinity of polyamides is measured by the thermal (DSC) measurement method, the crystallinity of polyolefins is measured by the X-ray diffraction method, and the crystallinity of other polymers (for example, polyesters) is measured by the density method. Each was measured.

-Cavity-
The void-containing resin molded body of the present invention contains long cavities inside with the length direction oriented in one direction, and is characterized by the void content and the aspect ratio of the voids.
The cavity means a vacuum domain or a gas phase domain existing inside the resin molded body.

The void content means the total volume of the contained cavities relative to the sum of the total volume of the solid phase portion of the resin molded body and the total volume of the contained cavities.
The void content is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, preferably 3% by volume or more and 50% by volume or less, and preferably 5% by volume to 40% by volume. % Is more preferable, and 10% by volume to 30% by volume is particularly preferable.
Here, the void content can be calculated based on the specific gravity by measuring the specific gravity.
Specifically, the void content can be obtained by the following equation (1).
Cavity content (%) = {1- (Density of cavity-containing resin molding after stretching) / (Density of polymer molding before stretching)} (1)

The aspect ratio refers to an average length of the cavity in the thickness direction orthogonal to the orientation direction of the cavity, r (μm), and an average length of the cavity in the orientation direction of the cavity, L (μm). L / r ratio is meant.
The aspect ratio is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. The aspect ratio is preferably 10 or more, more preferably 15 or more, and particularly preferably 20 or more. .

  2A to 2C are diagrams for specifically explaining the aspect ratio, in which FIG. 2A is a perspective view of the void-containing resin molded body, and FIG. 2B is A of the void-containing resin molded body in FIG. 2A. -A 'sectional drawing, FIG. 2C is BB' sectional drawing of the cavity containing resin molding in FIG. 2A.

  In the manufacturing process of the void-containing resin molded body, the void is usually oriented along the first stretching direction. Therefore, the “average length of the cavity (r (μm)) in the thickness direction perpendicular to the orientation direction of the cavity” is perpendicular to the surface 1a of the cavity-containing resin molded body 1 and in the first stretching direction. This corresponds to the average thickness r (see FIG. 2B) of the cavity 100 in a cross section at right angles (cross section AA ′ in FIG. 2A). The “average length (L (μm)) of the cavity in the orientation direction of the cavity” is a cross section perpendicular to the surface of the cavity-containing resin molded body and parallel to the first stretching direction (FIG. This corresponds to the average length L (see FIG. 2C) of the cavity 100 in the section BB ′ in 2A.

In addition, said 1st extending | stretching direction shows the extending direction of 1 axis | shaft, when extending | stretching is only 1 axis | shaft. Usually, since longitudinal stretching is performed along the direction in which the molded body flows during production, this longitudinal stretching direction corresponds to the first stretching direction.
Moreover, when extending | stretching is biaxial or more, at least 1 direction is shown among the extending directions aiming at cavity formation. Usually, even in stretching with two or more axes, longitudinal stretching is performed along the flow direction of the molded body during production, and a cavity can be formed by this longitudinal stretching. It corresponds to the first stretching direction.

  Here, the average length (r (μm)) of the cavities in the thickness direction orthogonal to the orientation direction of the cavities can be measured by an image of an optical microscope or an electron microscope. Similarly, the average length (L (μm)) of the cavities in the alignment direction of the cavities can be measured by an image of an optical microscope or an electron microscope.

The void-containing resin molded product of the present invention is characterized by the average number P of cavities in the film thickness direction, the refractive index difference ΔN between the crystalline polymer layer and the cavity layer, and the product of the ΔN and the P. have.
The number of cavities in the film thickness direction refers to the film thickness direction in a cross section perpendicular to the surface 1a of the void-containing resin molded body 1 and perpendicular to the first stretching direction (AA ′ cross section in FIG. 2A). Means the number of cavities 100 included in
The average number P of cavities in the film thickness direction is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, preferably 5 or more, more preferably 10 or more. Preferably, 15 or more are more preferable.
Here, the number of cavities in the film thickness direction can be measured by an image of an optical microscope or an electron microscope.

There is no restriction | limiting in particular as thickness of the said crystalline polymer layer (The cavity non-containing layer which does not contain a cavity), Although it can select suitably according to the objective, It is preferable that it is 1 micrometer or more on one side.
If the thickness of the crystalline polymer layer (void-free layer not containing cavities) is less than 1 μm, the cavity film may break.

There is no restriction | limiting in particular as thickness of the said cavity layer (cavity containing layer containing a cavity), Although it can select suitably according to the objective, It is preferable that it is 8 micrometers or more.
When the thickness of the cavity layer (cavity-containing layer containing a cavity) is less than 8 μm, the reflectance may be lowered.

Specifically, the difference in refractive index ΔN between the crystalline polymer layer and the cavity layer is defined as N1 and N2 when the refractive index of the crystalline polymer layer is N1 and the refractive index of the cavity layer is N2. It means a value of ΔN (= N1−N2) which is a difference.
Here, the refractive indexes N1 and N2 of the crystalline polymer layer and the cavity layer can be measured by an Abbe refractometer or the like.
The product of ΔN and P is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose, but is preferably 3 or more, more preferably 5 or more, and 7 or more. Particularly preferred.

  As described above, the void-containing resin molded body has various excellent characteristics in, for example, reflectance, glossiness, thermal conductivity, and the like due to the inclusion of the void. In other words, characteristics such as reflectance, glossiness, and thermal conductivity can be adjusted by changing the mode of the cavities contained in the cavities-containing resin molding.

-Glossiness-
The glossiness of the void-containing resin molded product is preferably 60 or more, more preferably 70 or more, and particularly preferably 80 or more.
Here, the glossiness can be measured by a variable glossmeter.

-Light transmittance-
The light transmittance of the void-containing resin molded article is preferably 0.4% or less, more preferably 0.3% or less, and particularly preferably 0.2% or less, at a wavelength of 550 nm. preferable.
Here, the light transmittance can be measured by a spectrophotometer.

-Thermal conductivity-
The thermal conductivity of the void-containing resin molded body is preferably 0.1 (W / mK) or less, more preferably 0.09 (W / mK) or less, and 0.08 (W / mK). mK) is particularly preferred.

Moreover, the suitable thermal conductivity of the said void containing resin molding can also be prescribed | regulated as a relative value. That is, the polymer composition identical to the polymer composition constituting the cavity-containing resin molded body having the same thickness as that of the cavity-containing resin molded body, where X (W / mK) is the thermal conductivity of the cavity-containing resin molded body. The X / Y ratio is preferably 0.27 or less, more preferably 0.2 or less, when the thermal conductivity of the polymer molded body containing no voids is Y (W / mK). It is preferably 0.15 or less.
Here, the thermal conductivity can be calculated by a product of measured values of thermal diffusivity, specific heat, and density. The thermal diffusivity can be generally measured by a laser flash method (for example, TC-7000 (manufactured by Vacuum Riko Co., Ltd.)). The specific heat can be measured by DSC according to the method described in JIS K7123. The density can be calculated by measuring the mass of a certain area and its thickness.

-Surface smoothness-
In addition, the void-containing resin molded article does not contain inorganic fine particles for expressing the void, incompatible resin, inert gas, etc. while containing the void, and thus has excellent surface smoothness. Have.
The surface smoothness of the void-containing resin molded body is not particularly limited and may be appropriately selected depending on the intended purpose. Ra = 0.3 μm or less is preferable, Ra = 0.25 μm or less is more preferable, and Ra = 0.1 μm or less is particularly preferable.

Furthermore, the cavity-containing resin molded body is characterized in that no cavity is formed not only on the surface of the molded body but also at a predetermined distance from the surface of the molded body.
That is, in the cross section orthogonal to the orientation direction of the cavity in the cavity-containing resin molded body, the 10 cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin molded body are measured from each center. A distance h (i) to the surface of the void-containing resin molded body is calculated, and an arithmetic average value h (avg) of each calculated distance h (i) is expressed by the following formula: h (avg)> T / 100 Satisfy the relationship.
However, T represents the arithmetic mean value of the thickness in the cross section, and the ten cavities are separated from any one straight line parallel to the thickness direction by 20 × T parallel to the one straight line. Are selected from cavities existing in a region sandwiched by other straight lines positioned at the same time.

The “center of the cavity” means the center when the cross-sectional shape of the cavity in the cross section is a perfect circle, and is arbitrarily set by, for example, the maximum square center method in the case of other shapes. The center of the circle that minimizes the sum of squares of the deviation from the reference circle is determined, and this is set as the center of the cavity.
The “surface of the void-containing resin molded body” means the outermost surface of the void-containing resin molded body in the thickness direction. Usually, it means the upper surface when the void-containing resin molded body is placed.

Specifically, a cross-section (see FIG. 2D) perpendicular to the surface of the void-containing resin molded body and perpendicular to the longitudinal stretching direction (see FIG. 2D) is appropriately magnified 300 to 3000 times using a scanning electron microscope. Microscope and take a cross-sectional picture. In the cross-sectional photograph, an arithmetic average value T of the thickness is calculated. As the arithmetic average value T of the thickness, the thickness measured using a long range contact displacement meter or the like may be used. In addition, FILM THICKNESS TESTER KG601B manufactured by Anritsu can be used for measuring the thickness.
Next, an arbitrary straight line parallel to the thickness direction is drawn in the cross-sectional photograph, and another straight line that is parallel to the single straight line and separated by 20 × T is drawn.
Then, in each cavity in the cross-sectional photograph, the center of a circle that minimizes the sum of squares of deviations from the reference circle arbitrarily set by the maximum square center method is determined, and this is set as the center of the cavity.
Then, in the region sandwiched between the one straight line and the other straight line, ten cavities having the shortest distance from the center of the cavity to the surface of the cavity-containing resin molded body are selected. The above-mentioned “distance from the center of the cavity to the surface of the cavity-containing resin molded body” means that when drawing a circle centered on the “center of the cavity”, the radius of the circle to be drawn is sequentially increased, The radius of the circle when it first contacts the surface of the void-containing resin molded body.
Then, for the 10 selected cavities, a distance h (i) from each center to the surface of the cavity-containing resin molded body is calculated, and an arithmetic average value h (avg) of each calculated distance h (i) Is calculated by the following equation (2).
h (avg) = (Σh (i)) / 10 (2)
The “distance h (i) from each center to the surface of the cavity-containing resin molded body” is to be accurately measured when the cavity-containing resin molded body is curved or stressed. Therefore, it is preferable that the measurement is performed in a state where it is placed in a flat shape.
The void-containing resin molded body has excellent surface smoothness since the void is not formed near the surface of the void-containing resin molded body while containing the void.

<Application>
Since the cavity-containing resin molded body of the present invention contains the cavity, for example, a lighting member for electronic equipment, a general household illumination member, a reflector such as an internal lighting signboard, a sublimation transfer recording material, or a thermal transfer recording material. Image receiving film material or image receiving sheet material, various heat insulating materials, pressure-sensitive recording materials, agricultural multi-films, cosmetic ingredients, food packaging materials, light-shielding shrink films, screens, etc. .

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are not intended to limit the present invention, and modifications may be made without departing from the spirit described above and below. Included in the technical scope.

Example 1
Polyethylene terephthalate (PET) as a crystalline polymer (Fuji Film Co., Ltd. product (synthetic product), glass transition temperature 70 ° C., melting point 255 ° C., intrinsic viscosity 0.66 dl / g), and 100 parts by mass as a crystal nucleating agent 0.8 parts by mass of the compound A of the following structural formula (1) is put into a lab plast mill μ (manufactured by Toyo Seiki Seisakusho Co., Ltd.), kneaded at 280 ° C., then extruded at a screw speed of 150 rpm, and a crystal nucleating agent A pellet containing (Compound A) was prepared.
The produced pellets were extruded from a T-die at 280 ° C. using a melt extruder and solidified with a casting drum at 53 ° C. to obtain a polymer film (unstretched film) having a crystallinity of 13% and a thickness of 214 μm. Obtained. This polymer film was uniaxially stretched (longitudinal stretch) by Roll to Roll.
Specifically, uniaxial stretching was performed at a peripheral speed (stretching speed) of 4 m / min in a heated atmosphere at 100 ° C.
By the stretching, a void was developed, and a void-containing resin film having a thickness of 54 μm, a crystallinity of 41% for the crystalline polymer, a reflectance of 90% for light having a wavelength of 550 nm, and a piercing strength of 5.4 N was obtained.

In addition, the measuring method of the crystallinity degree (%) of a crystalline polymer, the reflectance (%) with respect to light of 550 nm, and the piercing strength (N) is as follows.
-Method for measuring crystallinity of crystalline polymer-
The polyesters were measured by the density method. Specifically, the crystallinity was calculated using a density gradient tube method. A gradient tube was prepared with a carbon tetrachloride / n-heptane mixed solvent, and the density after 3 hours was measured at 25 ° C.
The degree of crystallinity was calculated by the following formula. d: Density of sample, dc: Crystal density, da: Amorphous density.
Crystallinity = dc (d−da) / d (dc−da)
PET: dc = 1.455, da = 1.335
PEN: dc = 1.407, da = 1.325
The value of was used.
On the other hand, polyamides were determined by thermal measurement (DSC) with reference to JP-A-10-273590.

-Measurement method of reflectance for 550nm light-
The reflectance of the reflective sheet was measured by measuring the reflectance at a wavelength of 550 nm by attaching an integrating sphere to a spectrophotometer (“V-570”; manufactured by JASCO). Here, as a reference value, the reflectance of the standard white board attached to the apparatus was set to 100%.

-Measuring method of piercing strength-
A metal (SUS440C) needle having a diameter of 1 mm and a tip curvature radius of 0.5 mm is pierced into a sample (measurement part: a circle having a diameter of 10 mm) fixed with a holder at a speed of 100 mm / min in the thickness direction. Measure the maximum load that opens. Assuming that the piercing strength is proportional to the thickness, the piercing strength per 30 μm thickness was determined.

(Example 2)
In Example 1, a polymer film was prepared in the same manner as in Example 1 except that 0.7 parts by mass of the compound B of the following structural formula (2) was used instead of 0.8 parts by mass of the compound A as a crystal nucleating agent. Obtained. The obtained polymer film had a crystallinity of 15% and a thickness of 170 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 120 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 42 μm, the crystallinity of the crystalline polymer is 28%, the reflectivity for light at 550 nm is 88%, and the penetration strength is 5.3N. A resin film was obtained.

(Example 3)
In Example 1, a polymer film was prepared in the same manner as in Example 1 except that 1.1 parts by mass of the compound C of the following structural formula (3) was used instead of 0.8 parts by mass of the compound A as a crystal nucleating agent. Obtained. The obtained polymer film had a crystallinity of 14% and a thickness of 207 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 110 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 51 μm, the crystallinity of the crystalline polymer is 35%, the reflectivity for light at 550 nm is 87%, and the piercing strength is 5.5 N A resin film was obtained.

Example 4
In Example 1, as a crystal nucleating agent, a polymer film was prepared in the same manner as in Example 1 except that 0.9 parts by mass of the compound D of the following structural formula (4) was used instead of 0.8 parts by mass of the compound A. Obtained. The polymer film obtained had a crystallinity of 16% and a thickness of 180 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 120 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 44 μm, the crystallinity of the crystalline polymer is 48%, the reflectance with respect to light at 550 nm is 88%, and the penetration strength is 5.3 N A resin film was obtained.

(Example 5)
In Example 1, instead of polyethylene terephthalate (PET) as a crystalline polymer, polyethylene naphthalate (PEN) (Fuji Film Co., Ltd. product (synthetic product), glass transition temperature 113 ° C., melting point 269 ° C., intrinsic viscosity 0 .62 dl / g), and in Example 1, instead of Compound A, Compound C was used as the crystal nucleating agent. In Example 1, the mixture was kneaded at 280 ° C. and then extruded at a screw speed of 150 rpm. Instead, after kneading at 300 ° C., a polymer film was obtained in the same manner as in Example 1 except that extrusion was performed at a screw speed of 160 rpm. The obtained polymer film had a crystallinity of crystalline polymer of 14% and a thickness of 110 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 170 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 27 μm, the crystallinity of the crystalline polymer is 24%, the reflectivity for light at 550 nm is 85%, and the piercing strength is 5.1 N A resin film was obtained.

(Example 6)
In Example 1, instead of polyethylene terephthalate (PET) as a crystalline polymer, polyethylene naphthalate (PEN) (Fuji Film Co., Ltd. product (synthetic product), glass transition temperature 113 ° C., melting point 269 ° C., intrinsic viscosity 0 .62 dl / g), and in Example 1, 1.1 parts by mass of Compound D was used instead of 0.8 parts by mass of Compound A as a crystal nucleating agent, and in Example 1, kneaded at 280 ° C. Then, instead of extruding at a screw speed of 150 rpm, a polymer film was obtained in the same manner as in Example 1 except that kneading was performed at 300 ° C. and extruding at a screw speed of 160 rpm. The obtained polymer film had a crystallinity of 18% and a thickness of 105 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 160 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 26 μm, the crystallinity of the crystalline polymer is 43%, the reflectance with respect to light at 550 nm is 83%, and the penetration strength is 5.0 N A resin film was obtained.

(Example 7)
In Example 1, instead of polyethylene terephthalate (PET), polyamide resin nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., glass transition temperature 85 ° C., melting point 243 ° C.) was used as the crystalline polymer. As a nucleating agent, 0.7 parts by mass of compound E (sodium dehydroabietic acid salt) is used in place of 0.8 parts by mass of compound A, and after kneading at 280 ° C. in Example 1, it is extruded at a screw speed of 150 rpm. Instead, after kneading at 240 ° C., a polymer film was obtained in the same manner as in Example 1 except that extrusion was performed at a screw speed of 25 rpm. The obtained polymer film had a crystallinity of the crystalline polymer of 23% and a thickness of 300 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 40 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 38 μm, the crystallinity of the crystalline polymer is 43%, the reflectivity for light at 550 nm is 91%, and the penetration strength is 6.1 N A resin film was obtained.

(Example 8)
In Example 1, instead of polyethylene terephthalate (PET), polyamide resin nylon MXD6 (manufactured by Mitsubishi Gas Chemical Co., Ltd., glass transition temperature 85 ° C., melting point 243 ° C.) was used as the crystalline polymer. As a nucleating agent, instead of compound A, compound E (dehydroabietic acid sodium salt) was used, and after kneading at 280 ° C. in Example 1, after kneading at 240 ° C. instead of extruding at a screw speed of 150 rpm A polymer film was obtained in the same manner as in Example 1 except that extrusion was performed at a screw speed of 25 rpm. The obtained polymer film had a crystallinity of 27% and a thickness of 410 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in a 100 degreeC heating atmosphere, and was carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in a 45 degreeC heating atmosphere. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 52 μm, the crystallinity of the crystalline polymer is 46%, the reflectance for light at 550 nm is 92%, and the penetration strength is 5.8 N A resin film was obtained.

(Comparative Example 1)
In Example 1, a polymer film was obtained in the same manner as in Example 1 except that the crystal nucleating agent (Compound A) was added instead of adding the crystal nucleating agent. The obtained polymer film had a crystallinity of 4% and a thickness of 150 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, but it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 25 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 41 μm, the crystallinity of the crystalline polymer is 7%, the reflectance for light at 550 nm is 89%, and the penetration strength is 3.2 N A resin film was obtained. In addition, the uniaxial stretching (longitudinal stretching) by Roll to Roll was difficult.

(Comparative Example 2)
In Example 1, instead of adding the crystal nucleating agent (Compound A), a polymer film and a void-containing resin film were obtained in the same manner as in Example 1 except that the crystal nucleating agent was not added. The obtained polymer film had a crystallinity of 4% and a thickness of 180 μm. Moreover, in Example 1, it replaced with the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 100 degreeC, it carried out similarly to Example 1 except having carried out the uniaxial stretching (longitudinal stretching) in the heating atmosphere of 110 degreeC. A void-containing resin film was obtained. The obtained void-containing resin film has a thickness of 22 μm, the crystallinity of the crystalline polymer is 28%, the reflectance with respect to light at 550 nm is 51%, and the piercing strength is 5.3N. A void-containing resin film was obtained.

(Comparative Example 3)
Example 1 was the same as Example 1 except that uniaxial stretching (longitudinal stretching) was attempted in a heated atmosphere at 25 ° C instead of uniaxial stretching (longitudinal stretching) in a heated atmosphere at 100 ° C. . As a result, uniaxial stretching (longitudinal stretching) by Roll to Roll could not be performed.

  Table 2 shows the production conditions of Examples 1 to 8 and Comparative Examples 1 to 3, the characteristics of the obtained polymer film (unstretched film), and the characteristics of the obtained void-containing resin film.

  Since the void-containing resin molded article of the present invention contains the void, for example, a reflection member such as a lighting member for electronic equipment, a general household lighting member, an internal lighting signboard, a sublimation transfer recording material, or a thermal transfer recording material. Image receiving film material or image receiving sheet material, various heat insulating materials, pressure-sensitive recording materials, agricultural multi-films, cosmetic ingredients, food packaging materials, light-shielding shrink films, screens, etc. .

DESCRIPTION OF SYMBOLS 1 Cavity containing resin molding 1a Surface 11 Raw material 12 Twin screw extruder / single screw extruder 13 T die 14 Casting drum 15 Longitudinal drawing machine 15a Roll 16 Lateral drawing machine 16a Clip 100 Cavity F Film or sheet L Cavity thickness at length r aspect ratio

Claims (7)

  A void-containing resin molded article comprising a polymer molded article containing a crystalline polymer and a crystal nucleating agent, and containing voids therein, wherein the crystallinity of the crystalline polymer in the void-containing resin molded article is 10% or more and 50% A void-containing resin molded product characterized by being less than.   The void-containing resin molded article according to claim 1, wherein the crystal nucleating agent is an organic crystalline nucleating agent.   The void-containing resin molded article according to any one of claims 1 to 2, wherein the content of the crystal nucleating agent with respect to the crystalline polymer is 0.01 mass% or more and less than 10 mass%.   The void-containing resin molded product according to any one of claims 1 to 3, wherein the crystalline polymer contains at least one of a crystalline polyester resin and a crystalline polyamide resin.   The void-containing resin molded article according to any one of claims 1 to 4, wherein the crystalline polyester resin contains at least one of polyethylene terephthalate resin and polyethylene naphthalate resin.   The void-containing resin molded product according to any one of claims 1 to 5, wherein the thickness of the void-free layer containing no void is 1 µm or more, and the thickness of the void-containing layer containing the void is 8 µm or more.   A method for producing a void-containing resin molded body for producing the void-containing resin molded body according to any one of claims 1 to 6, comprising a stretching step of stretching the polymer molded body at least uniaxially. When the stretching temperature is T (° C.), the glass transition temperature of the crystalline polymer is Tg (° C.), and the melting point of the crystalline polymer is Tm (° C.), Tg (° C.) <T (° C. ) <(Tm-50) (° C.).