JP6928765B2 - Resin composition for molding and molded product - Google Patents

Description

The present invention relates to a molding resin composition containing an ultraviolet absorbing polymer.

Conventionally, a resin molded product (hereinafter referred to as a molded product) has been used as a packaging material (packaging container) for pharmaceutical drugs and cosmetics. If light transmission is imparted to the molded product in order to visually recognize the contents, the contents are deteriorated by ultraviolet rays. Therefore, it has been practiced to add an ultraviolet absorber to the molded product. However, the UV absorber is easy to migrate and may contaminate the contents.
Therefore, Patent Documents 1 and 2 disclose resin compositions for molded articles containing polyolefins and resins incorporating an ultraviolet absorber.

JP 2001-72722 JP 2001-114842

However, when a molded product made of polyolefin is produced, the resin incorporating the ultraviolet absorber has poor compatibility with the polyolefin, is easily separated by ordinary mixing, and the strength of the molded product cannot be maintained. Therefore, the conventional composition has a problem that a desired compatibility can be secured only by synthesizing a resin in polyolefin.

An object of the present invention is to provide a molding resin composition capable of producing a molded product having good compatibility with polyolefin, less deterioration of the content due to ultraviolet rays, and less likely to contaminate the content.

The molding resin composition of the present invention contains a polyolefin (A) and an ultraviolet absorbing polymer (B).
The purple ultraviolet absorbing polymer (B) is a copolymer of a monomer represented by the following general formula (1) and a monomer mixture containing the monomer represented by the following general formula (2).

However, in the general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R ² represents an alkylene group having 1 to 6 carbon atoms or —O-R ⁵ , and R ⁵ represents an alkylene group having 1 to 6 carbon atoms. R ³ represents a hydrogen atom or a methyl group. X ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group or a nitro group.
In the general formula (2), R ¹⁶ represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.

According to the above invention, it is possible to provide a molding resin composition which has good compatibility with polyolefin, is less deteriorated by ultraviolet rays of the content, and can produce a molded product which is less likely to contaminate the content.

The molding resin composition (hereinafter referred to as a composition) of the present specification contains an ultraviolet-absorbing polymer (B) which is a copolymer of a polyolefin (A) and a monomer mixture containing a monomer having a specific structure. .. The monomer is an ethylenically unsaturated group-containing monomer.
Since the ultraviolet-absorbing polymer (B) has good compatibility with the polyolefin (A), the desired compatibility can be obtained without synthesizing the polymer in the polyolefin (A) as in the conventional case. Separately, the synthesized ultraviolet-absorbing polymer (B) and polyolefin (A) can be melt-kneaded and molded into a desired shape to prepare a molded product. When the obtained molded product is produced as a container, for example, it has good mechanical strength and can suppress contamination of the contents.

<Polyolefin (A)>
Polyolefin (A) is the main raw material of the composition, and examples thereof include polyethylene, polypropylene polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene, and copolymers thereof.
Examples of polyethylene include low-density polyethylene and high-density polyethylene.
Polypropylene includes, for example, crystalline or amorphous polypropines.
These copolymers include, for example, ethylene-propylene random, block or graft copolymers, α-olefin and ethylene or propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers. , Ethylene-ethyl acrylate copolymer, ethylene-acrylate copolymer and the like. Among these, crystalline or amorphous polypropylene, ethylene-propylene random, block or graft copolymers are preferable, and propylene-ethylene block copolymers are more preferable. Further, polypropylene is preferable from the viewpoint of being inexpensive and having a small specific gravity, so that the weight of the molded product can be reduced.
The number average molecular weight of the polyolefin (A) is preferably 30,000 to 200,000.

The melt flow rate (MFR) of the polyolefin (A) is preferably 1 to 100 (g / 10 minutes). The MFR is a numerical value obtained in accordance with JIS K-7210.

<Ultraviolet absorbing polymer (B)>
The ultraviolet-absorbing polymer (B) is a resin capable of absorbing ultraviolet rays. Further, since the ultraviolet absorbing polymer (B) is a resin, migration from the molded product to the contents is suppressed. Further, since the ultraviolet-absorbing polymer (B) uses a monomer having a specific structure as the monomer, it has good compatibility with the olefin (A), and the molded product has high transparency.

The ultraviolet-absorbing polymer (B) is a copolymer of a monomer represented by the following general formula (1) and a monomer represented by the following general formula (2). Since the ultraviolet-absorbing polymer (B) uses the monomer represented by the general formula (1) for synthesis, it can absorb ultraviolet rays.

General formula (1)

(In the formula, ^{R 1,} .R ² represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, an alkylene group or ^{-O-R 5,} 1 to 6 carbon atoms, ^{R 5} is a carbon Represents an alkylene group of numbers 1 to 6. R ³ represents a hydrogen atom or a methyl group. X ¹ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. , Cyano group or nitro group.)

In the general formula (1), the hydrocarbon group having 1 to 8 carbon atoms is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, or a heptyl. Chain hydrocarbon groups such as groups and octyl groups; alicyclic hydrocarbon groups such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; phenyl group, trill group, xsilyl group, benzyl group, Examples include aromatic hydrocarbon groups such as phenethyl groups.

The alkylene group having 1 to 6 carbon atoms includes, for example, a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group; a propylene group, a 2-methyltrimethylene group, and the like.
Examples thereof include a branched chain alkylene group such as a 2-methyltetramethylene group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a heptoxy group and the like.

The monomer represented by the general formula (1) is, for example, 2- [2'-hydroxy-5'-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-( Methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl -5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-Hydroxy-5'-(β-methacryloyloxyethoxy) -3'-tert-butylphenyl] -4-tert-butyl-2H-benzotriazole and the like can be mentioned.

The monomer represented by the general formula (1) can be used alone or in combination of two or more.

The content of the monomer represented by the general formula (1) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, based on 100% by mass of the monomer mixture. By containing an appropriate amount, it is easy to achieve both ultraviolet absorption and compatibility with the polyolefin (A).

Next, the ultraviolet-absorbing polymer (B) has improved compatibility with the polyolefin (A) by polymerizing the monomer represented by the general formula (2) in the synthesis.

General formula (2)

However, in the formula, R ¹⁶ represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 10 or more carbon atoms.
The monomer Z represented by the general formula (2) is a hydrocarbon group having 10 or more carbon atoms, and the ultraviolet-absorbing polymer (B) has a long-chain hydrophobic unit, so that the main chain is long. By having a hydrocarbon chain of the chain and improving the affinity with the highly hydrophobic polyolefin (A), the compatibility between the two is improved. The upper limit of the number of carbon atoms of Z is not limited as long as it can be copolymerized with the monomer represented by the general formula (1).

In the general formula (2), examples of the hydrocarbon group having 10 or more carbon atoms in Z include a linear structure, a branched structure, and a cyclic structure.
The hydrocarbon groups having a linear structure and a branched structure include, for example, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, and a henicosyl group. Examples thereof include a docosyl group, a tricosyl group, and an alkyl group of a tetracosyl group.
As the hydrocarbon group having a linear structure and a branched structure, a branched structure is preferable, and an isostearyl group is more preferable. The number of carbon atoms of the hydrocarbon groups having a linear structure and a branched structure is preferably 14 or more.

Examples of the hydrocarbon group having a cyclic structure (also referred to as a cyclic hydrocarbon group) include an alicyclic hydrocarbon group and a polycyclic hydrocarbon group.
Examples of the alicyclic hydrocarbon group include a cyclododecyl group and the like.
Examples of the polycyclic hydrocarbon group include an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group and the like. As these alicyclic hydrocarbon group and polycyclic hydrocarbon group, a polycyclic hydrocarbon group is preferable, and a dicyclopentanyl group is more preferable. The alicyclic hydrocarbon group is a group having one saturated or unsaturated carbon ring having no aromaticity, and the polycyclic hydrocarbon group is a saturated or unsaturated carbon having no aromaticity. It is a group having a plurality of rings.

The monomer represented by the general formula (2) is, for example, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, behenyl (meth) acrylate, dicyclopentanyl ( Examples thereof include meta) acrylate, dicyclopentenyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, and 2-ethyl-2-adamantyl (meth) acrylate. Among these, isostearyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate are preferable, and dicyclopentanyl (meth) acrylate is more preferable.

The monomer represented by the general formula (2) can be used alone or in combination of two or more.

The content of the monomer represented by the general formula (2) is preferably 30 to 97% by mass, more preferably 40 to 80% by mass in the monomer mixture. By containing an appropriate amount, it is easy to achieve both ultraviolet absorption and compatibility with the polyolefin (A).

The ultraviolet-absorbing polymer (B) preferably further polymerizes the monomer represented by the general formula (3). As a result, the light stability of the ultraviolet absorbing polymer (B) is further improved.

General formula (3)

(In the formula, R ⁹ represents a hydrogen atom or a cyano group, R ¹⁰ and R ¹¹ independently represent a hydrogen atom or a methyl group, R ¹² represents a hydrogen atom or a hydrocarbon group, and Y ¹ represents an oxygen atom. Or represents an imino group.)

The monomer represented by the general formula (3) is, for example, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6- Tetramethylpiperidin, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidin, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidin, 4- Cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-crotonoylamino-2,2 Examples thereof include 6,6-tetramethylpiperidin.

The monomer represented by the general formula (3) can be used alone or in combination of two or more.

The content of the monomer represented by the general formula (3) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, based on 100% by mass of the monomer mixture. By containing an appropriate amount, it is easy to achieve both photostability and compatibility with polyolefin (A).

The ultraviolet-absorbing polymer (B) preferably further polymerizes an aromatic vinyl monomer. As a result, the compatibility with the polyolefin (A) is further improved. Aromatic vinyl monomers include, for example, styrene, α-methylstyrene, vinyl benzoate, vinyltoluene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene. , Chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected by a group deprotectable by an acidic substance (for example, t-Boc) and the like.

In particular, it is highly preferable to use an aromatic vinyl monomer and a polycyclic hydrocarbon group in combination with the monomer mixture, whereby the compatibility with the polyolefin (A) is further improved.

The aromatic vinyl monomer can be used alone or in combination of two or more.

The content of the aromatic vinyl monomer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass, based on 100% by mass of the monomer mixture. By containing an appropriate amount, the compatibility with the polyolefin (A) is further improved.

The ultraviolet-absorbing polymer (B) can further polymerize other monomers. Other monomers are monomers other than those exemplified so far.

Other monomers include, for example, (meth) acrylic acid ester, crotonic acid ester, vinyl ester, maleic acid diester, fumaric acid diester, itaconic acid diester, (meth) acrylamide, vinyl ether, vinyl alcohol ester, and (meth) acrylonitrile. , Acid group-containing monomer.

The (meth) acrylic acid ester is, for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, n-butyl (meth) acrylic acid, ( Isobutyl acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, T-octyl acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) ) 2-methoxyethyl acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, (meth) Benzyl acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, (meth) acrylic Polyethylene Glycolic Acid Monomethyl Ether, (Meta) Polyethylene Glycol Acrylate Monoethyl Ether, (Meta) β-Phenoxyethoxyethyl Acrylic Acid, Nonyl Phenoxy Polyethylene Glycol (Meta) Acrylic Acid, Dicyclopentenyl (Meta) Acrylic Acid, (Meta) Dicyclopentenyloxyethyl acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic Examples thereof include tribromophenyl acid and tribromophenyloxyethyl (meth) acrylate.

Examples of the crotonic acid ester include butyl crotonic acid and hexyl crotonic acid.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate and the like. Examples of the maleic acid diester include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diester include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of the itaconic acid diester include dimethyl itaconic acid, diethyl itaconic acid, and dibutyl itaconic acid.

(Meta) acrylamide includes, for example, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-n-butyl. Acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N Examples thereof include -diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloyl morpholine, and diacetone acrylamide.

Examples of the vinyl ether include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like.

Acidic group-containing monomers include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid and carcinic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid and anhydrous. Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride, mesaconic acid or acid anhydrides thereof; trivalent or higher unsaturated polyvalent carboxylic acids or acid anhydrides thereof; monosuccinate (2-acryloyloxyethyl) ), Mono oxalic acid (2-methacryloyloxyethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), and other monovalent or higher polyvalent carboxylic acids [ (Meta) acryloyloxyalkyl] ester; mono (meth) acrylates of both terminal carboxypolymers such as ω-carboxy-polycaprolactone monoacrylate and ω-carboxy-polycaprolactone monomethacrylate can be mentioned.

Other monomers can be used alone or in combination of two or more.

Examples of the method for synthesizing the ultraviolet absorbing polymer (B) include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Of these, free radical polymerization and living radical polymerization are preferable.

For free radical polymerization, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound or a peroxide is preferable. Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), 2, 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis (2-hydroxymethylpropionitrile), or 2,2'-azobis [2- (2-imidazolin-2-yl)) Propane] and the like. Peroxides include, for example, benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate, di (2-ethoxyethyl) peroxy dicarbonate. , T-Butylperoxyneodecanoate, t-Butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.

The polymerization initiator can be used alone or in combination of two or more.

The reaction temperature of the synthesis is preferably 40 to 150 ° C, more preferably 50 to 110 ° C. The reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

In the living radical polymerization, side reactions that occur in general radical polymerization are suppressed, and further, the growth of the polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.

The living radical polymerization uses an organic halide or a sulfonyl halide compound as an initiator, and the atom transfer radical polymerization method using a transition metal complex as a catalyst can be applied to a wide range of monomers, and can be applied to existing equipment. It is preferable because the polymerization temperature can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in References 1 to 8 below.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Mattyjaszewski et al., Chem. Rev. 2001,101,2921
(Reference 3) Mattyjaszewski et al., J. Mol. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Sien
ce, 1996, 272,866
(Reference 5) International Publication No. 96/030421 (Reference 6) International Publication No. 97/018247 (Reference 7) Japanese Patent Application Laid-Open No. 9-208616 (Reference 8) Japanese Patent Application Laid-Open No. 8-411117

It is preferable to use an organic solvent for the synthesis of the ultraviolet-absorbing polymer (B). Organic solvents include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene. Examples thereof include glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

The organic solvent can be used alone or in combination of two or more.

The mass average molecular weight of the ultraviolet-absorbing polymer (B) is preferably 1,000 to 500,000, more preferably 3,000 to 15,000. The mass average molecular weight is a numerical value measured by gel permeation chromatography (GPC).

The blending amount of the ultraviolet absorbing polymer (B) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyolefin (A).

The compositions herein can contain wax.

Examples of the wax include polyethylene wax and polypropylene wax. The melting point of the wax is preferably 50 to 180 ° C, more preferably 80 to 170 ° C. The melting point of the wax is measured in a nitrogen atmosphere using a differential scanning calorimeter .

The number average molecular weight of the wax is preferably 500 to 25,000, more preferably 1000 to 15,000. The number average molecular weight is a numerical value measured in accordance with JIS K2207: 1996 (Japanese Industrial Standards).

The blending amount of the wax is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyolefin (A).

The composition of the present specification is preferably produced as, for example, a masterbatch containing a high concentration of the ultraviolet absorbing polymer (B). The masterbatch can be produced, for example, by melt-kneading the ultraviolet-absorbing polymer (B) and the polyolefin (A) and using a pelletizer to produce pellets. In order to prevent the agglomeration of the ultraviolet-absorbing polymer (B), a dispersion in which the ultraviolet-absorbing polymer (B) and wax are melt-kneaded in advance is prepared, and then melt-kneaded together with the polyolefin (A) in a masterbatch. It is preferable to prepare. Here, it is preferable to use a blend mixer, a three-roll mill, or the like for producing the dispersion.
The ultraviolet-absorbing polymer (B) is first pre-dispersed in a colored molding resin composition as a master batch and then blended (melted) with a thermoplastic resin of a diluted resin, rather than blending a considerable amount contained in the molded product at the time of molding. When a desired molded product is produced by kneading), the ultraviolet-absorbing polymer (B) can be easily uniformly dispersed in the molded product.
When the composition is prepared as a masterbatch, it is preferable to mix 1 to 30 parts by mass of the ultraviolet absorbing polymer (B) with respect to 100 parts by mass of the polyolefin (A). The mass ratio of the master batch (X) to the dilution resin (Y) used as the base resin of the molded product is preferably X / Y = 1/5 to 1/100. Within this range, the molded product can easily obtain good optical characteristics.

The dilution resin is not limited to polyolefin, and a thermoplastic resin having good compatibility with polyolefin (A) can be appropriately selected and used.

For melt kneading, for example, a single-screw kneading extruder, a twin-screw kneading extruder, a tandem twin-screw kneading extruder, or the like is preferably used. The melt-kneading temperature varies depending on the type of polyolefin (A), but is usually 15.
It is about 0 to 250 ° C.

The compositions herein can further include antioxidants, light stabilizers, dispersants and the like.

The molded article of the present specification includes a composition. Specifically, it is produced by molding a composition.
Examples of the molding method include extrusion molding, injection molding, blow molding and the like. Examples of the extrusion molding include compression molding, pipe extrusion molding, laminating molding, T-die molding, inflation molding, melt spinning and the like.

The molding temperature is usually 160 to 240 ° C., depending on the softening point of the diluted resin.

The molded product of the present specification varies in composition even when it is manufactured by high-speed extrusion molding (molding machine screw rotation speed: about 150 rpm), which has a faster molding speed than normal extrusion molding, or compression molding, which has a long shear-free region. Hard to occur. In particular, even in high-speed compression molding (production speed of 500 pieces / minute or more, in some cases 700 to 900 pieces / minute), which is about 10 times faster than injection molding, it is difficult for the molded product to vary in composition and contaminate the contents. It's hard to do.

Compression molding will be described as an example of the method for producing a molded product of the present specification. First, it comprises a step of melt-mixing the resin composition for coloring molding of the present invention, putting it into a compression molding machine, and obtaining a molded product by applying a pushing force by compression without applying a shearing force in the compression molding machine. This is a method for manufacturing a molded product. Here, when the force of pushing out by compression is applied without applying the shearing force, the colored molding resin composition exists in a state where the mixing force is not applied to the colored molding resin composition, that is, in the shear-free region. .. In the present invention, the molded product is obtained by putting a resin into a mold to obtain an article. Further, the molded product includes an article obtained without using a mold such as a plastic film and a molded product.

The molded products described in the present specification include, for example, medical agents, cosmetics, food containers and packaging materials, miscellaneous goods, textile products, pharmaceutical containers, various industrial coating materials, automobile parts, home appliances, building materials such as housing, etc. It can be widely used for toiletry products.

Hereinafter, the present invention will be described in more detail, but the present invention is not limited to these examples as long as it does not deviate from the technical idea of the present invention. In addition, "part by mass" is described as "part", and "mass%" is described as "%".

The polyolefins used in the examples are shown below. The number average molecular weights of the following polyolefins are all in the range of 30,000 to 200,000.
(A-1) Polyethylene (Suntech LD M2270, MFR = 7g / 10min, manufactured by Asahi Kasei Chemicals Co., Ltd.)
(A-2) Polyethylene (Novatec UJ790, MFR = 50g / 10min, manufactured by Japan Polyethylene Corporation)
(A-3) Polypropylene (Novatec PP FA3EB, MFR = 10.5g / 10min, manufactured by Japan Polypropylene Corporation)
(A-4) Polypropylene (Prime Polypro J226T, MFR = 20g / 10min, manufactured by Prime Polymer Co., Ltd.)
(A-5) Polyethylene (Evolu HSP65051B MFR = 0.45 g / 10
min, manufactured by Prime Polymer Co., Ltd.)

The wax used in the examples is shown below.
(D-1) Polyethylene wax (Sunwax 131-P number average molecular weight 3500, melting point 105 ° C, manufactured by Sanyo Chemical Industries, Ltd.)
(D-2) Polyethylene wax (high wax 405MP number average molecular weight 4500, melting point 120 ° C., manufactured by Mitsui Chemicals, Inc.)
(D-3) Polypropylene wax (High wax NP056, number average molecular weight 7200, melting point 130 ° C, manufactured by Mitsui Chemicals, Inc.)

[Production example of ultraviolet-absorbing polymer (B)]
Production of (Polymer (B-1)) 75.0 parts of methyl ethyl ketone was charged into a four-port separable flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 14 parts of RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.) as the monomer represented by the general formula (1), 43 parts of isostearyl acrylate and 43 parts of methyl methacrylate as the monomer represented by the general formula (2). After a uniform mixture of 5.0 parts of 2.2'-azobis (methyl isobutyrate) and 20.0 parts of methyl ethyl ketone, the mixture was charged into a dropping funnel. Then, the contents of the dropping funnel were dropped over 2 hours. After completion of the dropping, the reaction was continued for 2 hours. Then, sampling was performed to confirm that the polymerization yield was 98% or more, the mixture was cooled to 50 ° C., and the mixture was taken out into a Teflon (registered trademark) vat. Further, it was dried in a vacuum dryer at 50 ° C. for 12 hours to obtain a polymer (B-1).

RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.)

Production of (Polymer (B-2) to (B-27)) Same as Production Example 1 except that the type of monomer used in Production Example 1 and the amount used thereof were changed as shown in Table 1. The polymer (B-2) to the polymer (B-27) were obtained respectively.

The details of the terms in Table 1 are as follows.
・ Ultraviolet absorption monomer 1:
2- [2'-Hydroxy-3'-tert-butyl-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole / UV absorbing monomer 2:
2- [2'-Hydroxy-5'-(β-methacryloyloxyethoxy) -3'-ter
t-Butylphenyl] -4-tert-butyl-2H-benzotriazole

ADEKA STAB LA-82 (manufactured by ADEKA)

(Example 1)
[Manufacturing of masterbatch]
100 parts of wax (D-1) and 100 parts of polymer (B-1) were mixed and kneaded at 160 ° C. using a 3-roll mill to obtain a dispersion of polymer (B-1). Next, 10 parts of the above dispersion obtained together with 100 parts of polyolefin (A-1) was mixed with a Henschel mixer. Next, after melt-kneading at 180 ° C. with a single-screw extruder having a screw diameter of 30 mm, it was cut into pellets using a pelletizer to obtain a masterbatch.

[Film molding]
10 parts of the obtained masterbatch was mixed with 100 parts of polyolefin (A-1) as a diluted resin. Next, using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.), melt mixing was performed at a temperature of 180 ° C. and molding was performed to obtain a film having a thickness of 250 μm.

(Examples 2 to 53, Comparative Examples 1 to 4)
A masterbatch was produced in the same manner as in Example 1 except that the materials of Example 1 were changed to the materials and blending amounts shown in Table 2, and then the films of Examples 2 to 53 and Comparative Examples 1 to 4, respectively. Each was manufactured . In this specification, Examples 12 to 15 and Examples 36 to 39 are reference examples.

Details of the terms in Tables 2 and 3 are as follows.

ADEKA STAB LA-29 (manufactured by ADEKA)

[UV absorption]
The school annex transmittance of the obtained film was measured using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation criteria are as follows.
〇: Light transmittance of wavelength 290 to 360 nm is less than 2% over the entire region Good Δ: There is a region where light transmittance is 2% or more in a range of wavelength 290 to 360 nm Practical range ×: Light with wavelength 290 to 360 nm Transmittance is 2% or more over the entire area, impractical

[Film transparency]
The transparency of the obtained film was visually evaluated. The evaluation criteria are as follows.
⊚: No turbidity is observed. Excellent 〇: Almost no turbidity is observed. Good Δ: Some turbidity is observed. Practical range ×: Clearly turbidity is observed. Impractical

[Light resistance test]
The resulting film was exposed on a xenon weather meter at 300-400 nm with an illuminance of 60 W / m2 for 1500 hours. The evaluation criteria are as follows.
〇: No yellowing is observed. Good Δ: Slight yellowing is observed. Practical range ×: Yellowing is clearly observed. Impractical

[Migration evaluation]
The obtained film was sandwiched between soft vinyl chloride sheets and heat-pressed using a hot press under ^{the conditions of a pressure of 100 g / cm 2} and a temperature of 170 ° C. for 30 seconds. Then, the film was immediately removed and migration to a soft vinyl chloride sheet was evaluated using an ultraviolet-visible near-infrared spectrophotometer (manufactured by Shimadzu Corporation). The evaluation was carried out by selecting 5 points at arbitrary locations on the soft vinyl chloride sheet subjected to the above treatment, measuring the absorbance in the ultraviolet region, and calculating the average thereof.
◯: Absorbance at 280 to 480 nm is not detected (less than 0.05). Good Δ: Absorbance at 280 to 480 nm is 0.05 or more and 0.2 or less. Practical range ×: Absorbance at 280 to 480 nm exceeds 0.2. Impractical

Claims (6)

Contains polyolefin (A) with a number average molecular weight of 30,000 to 200,000 , and UV-absorbing polymer (B).
The ultraviolet-absorbing polymer (B) is a molding resin which is a copolymer of a monomer represented by the following general formula (1) and a monomer mixture containing a monomer represented by the following general formula (2). Composition.

(However, in the general formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ² represents an alkylene group having 1 to 6 carbon atoms or —OR ⁵ . , R ⁵ represents an alkylene group having 1 to 6 carbon atoms. R ³ represents a hydrogen atom or a methyl group. X ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. Represents 1 to 6 alkoxy groups, cyano groups or nitro groups.
In the general formula (2), R ¹⁶ represents a hydrogen atom or a methyl group. Z represents an isostearyl group or a cyclic hydrocarbon group having 10 or more carbon atoms. ) The molding resin composition according to claim 1, wherein the cyclic hydrocarbon group is a dicyclopentanyl group. The ultraviolet absorbent polymer (B), the monomer mixture in 100% by mass, including the general formulas total 30 to 97 wt% of the monomer represented by (2), for forming according to claim 1 or 2 Resin composition. The ultraviolet-absorbing polymer (B) according to any one of claims 1 to 3 , wherein the ultraviolet-absorbing polymer (B) contains a total of 3 to 30% by mass of the monomers represented by the general formula (1) in 100% by mass of the monomer mixture. Resin composition for molding. The molding resin composition according to any one of claims 1 to 4 , wherein the ultraviolet-absorbing polymer (B) contains a monomer represented by the following general formula (3) in the monomer mixture.
General formula (3)

(In the formula, R ⁹ represents a hydrogen atom or a cyano group, R ¹⁰ and R ¹¹ independently represent a hydrogen atom or a methyl group, R ¹² represents a hydrogen atom or a hydrocarbon group, and Y ¹ represents an oxygen atom. Or represents an imino group.) A molded product containing the molding resin composition according to any one of claims 1 to 5.