JP2021195435A - Resin composition and film - Google Patents

Abstract

To provide a resin composition which can suppress thermal degradation of an additive, and a film containing the same.SOLUTION: A resin composition has a blending ratio of an additive to a resin having a partial structure represented by the following general formula (I) or (II) of 50 mass% or less. In the formula (I), QA represents an ester bond represented in the formula; RA represents a substituent; n1 represents an integer of 1 to 5; * represents a bonding site with a balance of the repeating unit; and ** represents a bonding site with a phenyl group in the formula. In the formula (II), QB represents a connection group or a single bond other than an ester bond represented by QA in the formula (I); RB represents a substituent; n2 represents an integer of 1 to 5; and * represents a bonding site with a balance of the repeating unit. At least one RB represents a hydroxyl group.SELECTED DRAWING: None

Description

The present invention relates to resin compositions and films.

Thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, acrylonitrile butadiene styrene resin, and acrylic resin are used in various daily necessities and industrial products due to their good processability. It is a general-purpose resin. On the other hand, since these general-purpose resins have low heat resistance, it is often difficult to use them in applications that require heat resistance. Instead, resins having a high melting point such as engineering plastics and super engineering plastics are used. There is. However, these engineering plastics have disadvantages such as poor workability and low solubility in general organic solvents, which makes them difficult to use in thin film applications such as coating films.

In addition, when using a resin, it is common to prepare and use a resin composition by mixing various additives with the resin according to the application, such as improvement of workability and weather resistance. ing. Therefore, the additive also needs to have heat resistance that can sufficiently withstand the processing temperature and the operating temperature of the resin composition. In order to increase the heat resistance of the additive, for example, Patent Documents 1 to 3 disclose a technique for increasing the molecular weight of the additive.

Japanese Unexamined Patent Publication No. 10-338777 Japanese Unexamined Patent Publication No. 2003-40937 International Publication No. 2008/062860

As described above, various additives with improved heat resistance have been developed, but the additives are decomposed to some extent at high temperatures, and it is difficult to fully exert their functions. In addition, the thermal decomposition products of the additives often accelerate the deterioration of the resin. Under such circumstances, it is desired to develop a resin composition that meets the high heat resistance requirements in recent years.

Therefore, an object of the present invention is to provide a resin composition capable of suppressing thermal deterioration of additives and a film containing the same.

As a result of diligent studies by the present inventors, it is important to use a specific resin having excellent heat resistance and to adjust the compounding ratio of the additive to the specific resin within a specific range in order to solve the above-mentioned problems. It was found that the present invention was developed.
The present invention is, for example, as follows.

式（Ｉ）中、Ｑ_Ａは式中に示されるエステル結合を表し、Ｒ_Ａは置換基を表し、ｎ１は１〜５の整数を表し、＊は前記繰り返し単位の残部との結合部位を表し、＊＊は式中のフェニル基との結合部位を表す。

式（ＩＩ）中、Ｑ_Ｂは式（Ｉ）中のＱ_Ａで表されるエステル結合以外の連結基又は単結合を表し、Ｒ_Ｂは置換基を表し、ｎ２は１〜５の整数を表し、＊は前記繰り返し単位の残部との結合部位を表す。但し、少なくとも１つのＲ_Ｂは水酸基を表す。
［２］
上記樹脂中の上記繰り返し単位の含有率が、上記樹脂中の全繰り返し単位に対し２モル％以上５０モル％以下である、［１］に記載の樹脂組成物。
［３］
上記繰り返し単位が、（メタ）アクリレート系モノマー由来の繰り返し単位、（メタ）アクリルアミド系モノマー由来の繰り返し単位、およびＮ−置換マレイミド系モノマー由来の繰り返し単位のいずれかである、［１］又は［２］に記載の樹脂組成物。
［４］
上記樹脂が上記繰り返し単位に加え、炭素数１〜５個の直鎖又は分岐アルキル基を側鎖に有する（メタ）アクリレート系繰り返し単位、及び／又は、フェノール性水酸基以外の水酸基を側鎖に有する（メタ）アクリレート系繰り返し単位を更に含有する、［１］〜［３］のいずれか１項に記載の樹脂組成物。
［５］
上記樹脂が上記繰り返し単位に加え、オレフィン系繰り返し単位を更に含有する、［１］〜［３］のいずれか１項に記載の樹脂組成物。
［６］
上記樹脂が上記繰り返し単位に加え、ハロゲン原子含有繰り返し単位を更に含有する、［１］〜［３］のいずれか１項に記載の樹脂組成物。
［７］
［１］〜［６］のいずれか１項に記載の樹脂組成物を含むフィルム。 [1]
A resin composition containing a resin containing a repeating unit having a partial structure represented by the following general formula (I) or (II) and an additive, and the compounding ratio of the additive to the resin is 50% by mass or less. thing.

In formula (I), Q _A represents the ester bond shown in the formula, _RA represents a substituent, n1 represents an integer of 1-5, and * represents the binding site with the rest of the repeating unit. , ** represent the binding site with the phenyl group in the formula.

Wherein (II), _{Q B} represents a linking group or a single bond other than an ester bond represented by _{Q A} in the formula (I), _{R B} represents a substituent, n2 is an integer of 1 to 5 , * Represent the binding site with the rest of the repeating unit. Provided that at least one of _{R B} represents a hydroxyl group.
[2]
The resin composition according to [1], wherein the content of the repeating unit in the resin is 2 mol% or more and 50 mol% or less with respect to all the repeating units in the resin.
[3]
The repeating unit is either a repeating unit derived from a (meth) acrylate-based monomer, a repeating unit derived from a (meth) acrylamide-based monomer, or a repeating unit derived from an N-substituted maleimide-based monomer, [1] or [2]. ] The resin composition according to.
[4]
In addition to the repeating unit, the resin has a (meth) acrylate-based repeating unit having a linear or branched alkyl group having 1 to 5 carbon atoms in the side chain, and / or a hydroxyl group other than the phenolic hydroxyl group in the side chain. The resin composition according to any one of [1] to [3], further containing a (meth) acrylate-based repeating unit.
[5]
The resin composition according to any one of [1] to [3], wherein the resin further contains an olefin-based repeating unit in addition to the repeating unit.
[6]
The resin composition according to any one of [1] to [3], wherein the resin further contains a halogen atom-containing repeating unit in addition to the repeating unit.
[7]
A film containing the resin composition according to any one of [1] to [6].

INDUSTRIAL APPLICABILITY According to the present invention, it has become possible to provide a resin composition capable of suppressing thermal deterioration of additives and a film containing the same.

Hereinafter, embodiments for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.
The resin composition according to the present embodiment contains a specific resin having excellent heat resistance and an additive, and the compounding ratio of the additive to the resin is adjusted to 50% by mass or less. When a resin with low heat resistance, such as a thermoplastic resin commonly used in daily necessities and industrial products, is used, it has excellent heat resistance because it accelerates the thermal deterioration of the additive used in combination with the pyrolysis product of the resin. It becomes difficult to obtain a resin composition to which the desired function is imparted. In the resin composition according to the present embodiment, which comprises a specific resin having excellent heat resistance described in detail below and an additive whose blending ratio with respect to the resin is adjusted to a specific range, the heat of the additive is used. Since deterioration is suppressed, a resin composition having excellent heat resistance and a desired function can be obtained.

<Resin>
The resin contained in the resin composition according to the present embodiment (hereinafter, simply referred to as “resin”) is a repeating unit having a partial structure represented by the following general formula (I) or (II) (hereinafter, hereinafter,). It contains a "repeating unit (a)").

In formula (I), Q _A represents the ester bond shown in the formula, _RA represents a substituent, n1 represents an integer of 1-5, and * represents the binding site with the rest of the repeating unit. , ** represent the binding site with the phenyl group in the formula.

_{Examples of the substituent represented by RA} include an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 6 carbon atoms), and an alkoxy group (for example, an alkoxy group). Examples thereof include a methoxy group or an ethoxy group), a hydroxyl group, an acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, a halogen atom and the like. n1 represents an integer of 1 to 5 as described above, and may be an integer of 1 to 3. If n1 is an integer of 2 or more, R _A is may be the same there are a plurality, may be different.

Wherein (II), _{Q B} represents a linking group or a single bond other than an ester bond represented by _{Q A} in the formula (I), _{R B} represents a substituent, n2 is an integer of 1 to 5 , * Represent the binding site with the rest of the repeating unit. Provided that at least one of _{R B} represents a hydroxyl group.

Q _B, as described above, represents a linking group or a single bond other than an ester bond represented by _{Q A,} the linking groups other than an ester bond represented by _{Q A,} for example, -CONR- (R is It represents a hydrogen atom or an alkyl group), an alkylene group (for example, an alkylene group having 1 to 4 carbon atoms), a urethane bond, an ether bond, and an ester bond represented by * -O-CO-** (** is. The binding site with the phenyl group in the formula (II) is represented.) And the like.

Examples of the substituent represented by R _B, for example, an alkyl group (e.g., alkyl group having 1 to 5 carbon atoms), a cycloalkyl group (e.g., cycloalkyl group having 3 to 6 carbon atoms), alkoxy groups (e.g., methoxy group, ethoxy group), a hydroxyl group, (acetyl group, a nitro group, a cyano group, a carboxyl group, an amino group, an ester group, and a halogen atom. However, as described above, at least one of R _B represents a hydroxyl group ..

n2 represents an integer of 1 to 5 as described above, or may be an integer of 1 to 3. If n2 is an integer of 2 or more, to the R _B, which are present in plural, it may be the same or may be different.

The repeating unit (a) may have a partial structure represented by the above-mentioned general formula (I) or (II), but may be, for example, a repeating unit derived from a (meth) acrylate-based monomer. , It may be a repeating unit derived from a (meth) acrylamide-based monomer, it may be a repeating unit derived from an N-substituted maleimide-based monomer, or it may be a repeating unit derived from a styrene-based monomer.

When the repeating unit (a) is a repeating unit derived from a (meth) acrylate-based monomer, the (meth) acrylate-based monomer may be, for example, 4-methoxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2 , 6-di-tert-butylphenyl (meth) acrylate, 2,6-di-tert-butyl-4-methoxyphenyl (meth) acrylate, 2-tert-butyl-4-hydroxyphenyl (meth) acrylate, 3- tert-butyl-4-hydroxyphenyl (meth) acrylate, 2,6-di-tert-butyl-4-methylphenyl (meth) acrylate, 2-hydroxy-4-tert-butylphenyl (meth) acrylate, 2,4 -Di-methyl-6-tert-butylphenyl (meth) acrylate and the like can be mentioned.

When the repeating unit (a) is a repeating unit derived from a (meth) acrylamide-based monomer, examples of the (meth) acrylamide-based monomer include N- (4-hydroxyphenyl) (meth) acrylamide and the like.

When the repeating unit (a) is a repeating unit derived from an N-substituted maleimide-based monomer, examples of the N-substituted maleimide-based monomer include 4-hydroxyphenylmaleimide and 3-hydroxyphenylmaleimide.

When the repeating unit (a) is a repeating unit derived from a styrene-based monomer, examples of the styrene-based monomer include α-methyl-p-hydroxystyrene.

In the present embodiment, the resin is preferably a binary or ternary copolymer containing one or more repeating units different from the repeating unit (a). In this case, the content of the repeating unit (a) in the resin is preferably in the range of 2 mol% or more and 50 mol% with respect to all the repeating units in the resin. When the content of the repeating unit (a) in the resin is 2 mol% or more, the thermal decomposition of the resin and the additive used in combination can be suppressed more effectively.

When the content of the repeating unit (a) in the resin is 50 mol% or less, yellowing of the resin occurs during heating while maintaining the effect of suppressing thermal decomposition of the resin and the additive used in combination. It is possible to effectively suppress the resin from becoming hard and brittle. From the same viewpoint, the content of the repeating unit (a) in the resin may be 2 mol% or more and 30 mol% or less, or 2 mol% or more and 20 mol% or less.

In the present embodiment, the repeating unit different from the repeating unit (a) (hereinafter, referred to as “copolymer component”) that can be contained when the resin is a copolymer is, for example, a (meth) acrylate type. Examples thereof include a repeating unit, an olefin-based repeating unit, a halogen atom-containing repeating unit, a styrene-based repeating unit, a vinyl acetate-based repeating unit, and a vinyl alcohol-based repeating unit.

As the (meth) acrylate-based repeating unit which is a copolymerization component, for example, a repeating unit derived from a (meth) acrylate-based monomer having a linear or branched alkyl group in the side chain and a hydroxyl group (excluding phenolic hydroxyl group) are side chains. Examples thereof include repeating units derived from the (meth) acrylate-based monomer contained in the above.

Examples of the (meth) acrylate-based repeating unit having a linear or branched alkyl group in the side chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and isopropyl (meth) acrylate. , (Meta) butyl acrylate, (meth) isobutyl acrylate, (meth) s-butyl acrylate, (meth) t-butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, (meth) Heptyl acrylate, (meth) octyl acrylate, (meth) isooctyl acrylate, (meth) 2-ethylhexyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, (meth) ) Isodecyl acrylate, (meth) undecyl acrylate, (meth) dodecyl acrylate, (meth) tridecyl acrylate, (meth) tetradecyl acrylate, (meth) myristyl acrylate, (meth) pentadecyl acrylate, (meth) Examples thereof include monomer-derived components such as hexadecyl acrylate, heptadecyl (meth) acrylate, and octadecyl (meth) acrylate. These may be used alone or in combination of two or more. Among the above, a (meth) acrylate-based repeating unit having a linear or branched alkyl group having 1 or more and 4 or less carbon atoms in the side chain can be preferably used.

Examples of the (meth) acrylic repeating unit having a hydroxyl group other than the phenolic hydroxyl group in the side chain include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxypropyl (meth) acrylate. Examples thereof include monomer-derived components such as hydroxybutyl and 6-hydroxyhexyl (meth) acrylic acid. These may be used alone or in combination of two or more.

Examples of the olefin-based repeating unit as a copolymerization component include components derived from olefin-based monomers such as ethylene, propylene, isoprene, and butadiene. These may be used alone or in combination of two or more.

Examples of the halogen atom-containing repeating unit as a copolymerization component include monomer-derived components such as vinyl chloride and vinylidene chloride. These may be used alone or in combination of two or more.

Examples of the styrene-based repeating unit as the copolymerization component include components derived from styrene-based monomers such as styrene, α-methylstyrene, and vinyltoluene. These may be used alone or in combination of two or more.

The copolymer may have any structure of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. If the structure of the copolymer is a random copolymer, the production process and preparation with a cyanine dye are easy. Therefore, the random copolymer is preferable to other copolymers.

Radical polymerization can be used as a polymerization method for obtaining a copolymer. Radical polymerization is preferable because it is easy to produce industrially. The radical polymerization may be a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method or the like. It is preferable to use a solution polymerization method for radical polymerization. By using the solution polymerization method, it is easy to control the molecular weight of the copolymer.

In radical polymerization, the above-mentioned monomer may be diluted with a polymerization solvent, and then a polymerization initiator may be added to polymerize the monomer.
The polymerization solvent may be, for example, an ester solvent, an alcohol ether solvent, a ketone solvent, an aromatic solvent, an amide solvent, an alcohol solvent, or the like. The ester solvent may be, for example, methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, ethyl lactate and the like. The alcohol ether solvent is, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-. It may be 3-methyl-1-butanol or the like. The ketone solvent may be, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or the like. The aromatic solvent may be, for example, benzene, toluene, xylene and the like. The amide-based solvent may be, for example, formamide, dimethylformamide, or the like. The alcohol solvent may be, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol, t-butanol, diacetone alcohol, 2-methyl-2-butanol and the like. .. In the above-mentioned polymerization solvent, one kind may be used alone, or two or more kinds may be mixed and used.

In radical polymerization, the amount of the polymerization solvent used is not particularly limited, but when the total amount of the monomers is set to 100 parts by mass, the amount of the polymerization solvent used is preferably 1 part by mass or more and 1000 parts by mass or less. It is more preferably 10 parts by mass or more and 500 parts by mass or less.

The radical polymerization initiator may be, for example, a peroxide and an azo compound. The peroxide may be, for example, benzoyl peroxide, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butyl peroxide and the like. The azo compounds include, for example, azobisisobutyronitrile, azobisamidinopropane salt, azobiscyanovaleric acid (salt), and 2,2'-azobis [2-methyl-N- (2-hydroxyethyl)). Propionamide] and the like.

The amount of the radical polymerization initiator used is preferably 0.0001 part by mass or more and 20 parts by mass or less, and 0.001 part by mass or more and 15 parts by mass or less when the total amount of the monomers is set to 100 parts by mass. It is more preferably 0.005 part by mass or more and 10 parts by mass or less. The radical polymerization initiator may be added to the monomer and the polymerization solvent before the initiation of the polymerization, or may be added dropwise to the polymerization reaction system. It is preferable to drop the radical polymerization initiator into the polymerization reaction system with respect to the monomer and the polymerization solvent in that the heat generation due to the polymerization can be suppressed.

The reaction temperature of the radical polymerization is appropriately selected depending on the type of the radical polymerization initiator and the polymerization solvent. The reaction temperature is preferably 60 ° C. or higher and 110 ° C. or lower from the viewpoint of ease of manufacture and reaction controllability.

<Additives>
In the resin composition according to the present embodiment, in order to realize the effect of suppressing thermal deterioration of the additive by using the resin containing the repeating unit (a) and having excellent heat resistance, the additive is added in an amount of 50% by mass based on the resin. It is contained in the following compounding ratio. The compounding ratio of the additive to this resin may be 30% by mass or less, or may be 10% by mass or less. The lower limit of the blending ratio of the additive can be appropriately set according to the purpose of use of the additive, the desired function, and the like, and is not particularly limited. As an example, the lower limit of the compounding ratio of the additive may be 0.01% by mass or more. The resin composition according to the present embodiment may contain one kind of additive alone or two or more kinds of additives. When the resin composition according to the present embodiment contains two or more kinds of additives, the above-mentioned compounding ratio indicates the total mass ratio of the additives to the resin.

In the present embodiment, the additive is added to the resin in the above-mentioned compounding ratio for the purpose of maintaining the function of the resin or imparting a new function, and means an organic additive. Here, the "organic additive" is an additive selected from compounds containing carbon atoms, and may be a low molecular weight compound, a high molecular weight compound, or an oligomer. Organic metal salts are also included.
However, the additive does not chemically react with the resin and is assumed to be present in the composition with the same chemical structure as when it was added, and is a cross-linking agent or a curing agent that crosslinks the resin chains with heat or light. Does not include.
Specific examples of the additives are shown in Table 1.

The resin composition according to the present embodiment is suitably used as a thin film application such as a coating film, a film substrate, and an adhesive layer used when bonding film substrates to each other in various applications requiring heat resistance. be able to. For example, gas barrier films for packaging materials for foods, medical supplies, chemicals, etc., optical films used for security products with anti-counterfeiting structures, coating films (surface protective layers) used for building materials sheets such as decorative sheets, and liquid crystals. Examples include color filters used in displays and the like.

<Synthesis of resin (group a)>
Synthesis Example 1: Synthesis of resin P-1a 80 parts by mass of cyclohexanone was prepared as a polymerization solvent. In addition, 85 parts by mass of methyl methacrylate (MMA) and 15 parts by mass of 4-methoxyphenyl methacrylate (MPhMA) were prepared as acrylic monomers. Further, 0.22 parts by mass of benzoyl peroxide (BPO) was prepared as a polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux tube, and the mixture was stirred and refluxed for 8 hours while being heated to 80 ° C. while introducing nitrogen gas into the reaction vessel. As a result, a polymer solution containing an acrylic copolymer formed from a repeating unit derived from MMA and a repeating unit derived from MPhMA was obtained. The obtained polymer solution was added dropwise to a large amount of methanol, reprecipitated and purified, and dried under reduced pressure at room temperature for 24 hours to obtain the resin P-1a described below.

Synthesis of Resin P-2a Resin P-, which will be described later, is the same as in Synthesis Example 1 except that 4-hydroxyphenyl methacrylate (HPMA) is used instead of 4-methoxyphenyl methacrylate (MPhMA). 2a was obtained.

Synthesis of resin P-3a After synthesis example 1, the same method as in synthesis example 1 was used except that N- (4-hydroxyphenyl) methacrylamide (HPMAA) was used instead of 4-methoxyphenyl methacrylate (MPhMA). The above resin P-3a was obtained.

Synthesis of Resin P-4a Resin P-4a described below was prepared in the same manner as in Synthesis Example 1 except that 4-hydroxymaleimide (HPhMI) was used instead of 4-methoxyphenyl methacrylate (MPhMA). Got

Synthesis of Resin P-101a For comparison, the resin P-101a described later was obtained in the same manner as in Synthesis Example 1 except that 4-methoxyphenyl methacrylate (MPhMA) was not used.

Synthesis of Resin P-102a For comparison, the resin P described below was prepared in the same manner as in Synthesis Example 1 except that phenyl methacrylate (PhMA) was used instead of 4-methoxyphenyl methacrylate (MPhMA) in Synthesis Example 1. -102a was obtained.

Synthesis of Resin P-103a For comparison, the resin P- shown below is the same as in Synthesis Example 1 except that styrene (St) is used instead of 4-methoxyphenyl methacrylate (MPhMA). Obtained 103a

<Evaluation>
(Evaluation 1) Evaluation of heat resistance of resin For each of the resins synthesized above, the mass reduction rate (%) under an air atmosphere and a nitrogen atmosphere was measured by the following method. A differential thermogravimetric simultaneous measuring device (STA7000, manufactured by Hitachi High-Tech Science Co., Ltd.) was used to measure the mass reduction rate (%). The sample is heated at 250 ° C. for 20 minutes in an air atmosphere or a nitrogen atmosphere, and the mass reduction amount (M = M _{0 −} M ₁ ) obtained by subtracting the mass (M _{1 ) after heating from the initial mass (M 0) before heating.} Was divided by the initial mass (M ₀ ) to calculate the mass reduction rate ([M / M ₀ ] × 100) (%). The lower the mass reduction rate, the better the heat resistance.

"A" is when the mass reduction rate is less than 20% in both the measurement under the air atmosphere and the nitrogen atmosphere, and the mass loss rate is 20% or more in one or both measurements under the air atmosphere and the nitrogen atmosphere. The case was set to "B". The results are shown in Table 2.

(Evaluation 2) Evaluation of ability to suppress thermal deterioration of additives A resin solution was prepared by dissolving 20 parts by mass of the obtained resin in 80 parts by mass of cyclohexanone. Add a hindered amine-based light stabilizer (trade name: Tinuvin (registered trademark) 123, manufactured by BASF Japan Ltd.) or tris (pentafluoroethyl) trifluorophosphate (FAP) as an additive to the obtained resin solution. A resin solution was obtained by adding 0.1 parts by mass of a cyanine dye having a counter anion and having a structure represented by the following formula (1). The above resin solution was applied onto a glass substrate using spin coating, heated on a hot plate set at 200 ° C. for 10 minutes and dried to form a coating film having a thickness of 1 μm.

The glass substrate on which the coating film was formed was heated at 250 ° C. for 10 minutes, and the residual ratio of the additive in the coating film was measured. A glass substrate was ^{cut into a size of 1 cm 2} , immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. Addition into glass substrate extract by ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System) The agent was quantified. The additive residual ratio ([V ₁ / V ₀ ] × 100) (%) was calculated by dividing the amount of the additive remaining after heating (V ₁ ) by the initial amount of the additive (V _{0) before heating.} The higher the residual ratio of the additive, the better the ability to suppress the thermal deterioration of the additive.

In the measurement of both the resin composition to which the hindered amine light stabilizer is added and the resin composition to which the cyanine pigment is added, the case where the residual additive ratio is 90% or more is "A", and in one or both measurements. The case where the residual additive ratio was less than 90% was defined as "B". The results are shown in Table 2.

<Synthesis of resin (group b)>
Synthesis Example 2: Synthesis of resin P-1b An autoclave reactor with an internal volume of 300 mL is prepared, and 20 mL of a methanol solution of 50% by mass of 4-methoxyphenyl methacrylate (MPhMA) and 1 g of t-butyl hydroperoxide as a polymerization initiator are added. , Dissolved. After degassing the inside of the reactor, ethylene gas was introduced into the reactor to produce a copolymer at a pressure of 100 bar and a polymerization temperature of 175 ° C. The obtained copolymer was dissolved in xylene and reprecipitated with methanol to obtain the resin P-1b described later.

Synthesis of Resin P-2b Resin P-, which will be described later, is the same as in Synthesis Example 2 except that 4-hydroxyphenyl methacrylate (HPMA) is used instead of 4-methoxyphenyl methacrylate (MPhMA). 2b was obtained.

Synthesis of Resin P-101b For comparison, the resin P-101b described later was obtained in the same manner as in Synthesis Example 2 except that 4-methoxyphenyl methacrylate (MPhMA) was not used.

Synthesis of Resin P-102b For comparison, the resin P shown below is in the same manner as in Synthesis Example 2 except that benzyl methacrylate (BzMA) is used instead of 4-methoxyphenyl methacrylate (MPhMA) in Synthesis Example 2. -102b was obtained.

(Evaluation 3) Evaluation of heat resistance of the resin The heat resistance of each of the resins synthesized above was evaluated by the same method as in Evaluation 1 above. The results are shown in Table 3.

(Evaluation 4) Evaluation of ability to suppress thermal deterioration of additives 1 g of each resin synthesized above, hindered amine-based light stabilizer (trade name: Chinubin 123, manufactured by BASF Japan Ltd.), or Tris (pentafluoro) Ethyl) Trifluorophosphate (FAP) was mixed with 0.01 g of a cyanine dye having the structure represented by the above formula (1) as a counter anion. The mixture of the obtained resin and the additive was placed on a glass substrate, and the glass substrate was heated on a hot plate at 200 ° C. for 10 minutes. An aluminum block heated to 200 ° C. was placed on the molten mixture and pressed with a force of 20 kgf for 10 seconds, and then rapidly cooled to room temperature. The pressed sheet-like mixture was peeled off from the glass substrate, immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. Addition into glass substrate extract by ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System) The agent was quantified. The additive residual ratio ([V ₁ / V ₀ ] × 100) (%) was calculated by dividing the amount of the additive remaining after heating (V ₁ ) by the initial amount of the additive (V _{0) before heating.} The higher the residual ratio of the additive, the better the ability to suppress the thermal deterioration of the additive.

In the measurement of both the resin composition to which the hindered amine-based light stabilizer was added and the resin composition to which the cyanine pigment was added, the case where the residual additive ratio was 90% or more was "A", and in one or both measurements. The case where the residual additive ratio was less than 90% was defined as "B". The results are shown in Table 3.

<Synthesis of resin (group c)>
Synthesis Example 3: Synthesis of resin P-1c An autoclave type reactor having an internal volume of 300 mL was prepared, and 0.1 g of potassium persulfate, 1.0 g of sodium lauryl sulfate, and partially saponified polyvinyl alcohol (polymerization degree 500, saponification degree 98.6). %), 12 mL of 10% aqueous solution and 50 mL of water were added and dissolved. 25 g of vinyl chloride monomer was added and reacted at 45 ° C. for 7 hours to obtain an emulsion solution. The emulsion solution was freeze-dried to recover the polyvinyl chloride precipitate, washed with warm water, and then dried under reduced pressure. The obtained powder was dissolved in tetrahydrofuran, and polyvinyl alcohol, which was an insoluble matter, was removed by filtration. This tetrahydrofuran solution was poured into a large amount of methanol and the precipitate was filtered off to give polyvinyl chloride (PVC).

0.8 g of the obtained PVC was dissolved in 10 mL of cyclohexanone, 0.2 g of 4-hydroxyphenyl methacrylate (HPMA) and 0.02 g of benzoyl peroxide were added, and the mixture was reacted at 80 ° C. for 8 hours under a nitrogen atmosphere. The obtained reaction solution was poured into a large amount of methanol, and the precipitate was filtered off to obtain a polyvinyl chloride-based graft copolymer P-1c containing the repeating unit described later.

Synthesis of Resin P-2c In the same manner as in Synthesis Example 3, except that N- (4-hydroxyphenyl) methacrylamide (HPMAA) was used instead of 4-hydroxyphenyl methacrylate (HPMA) for Synthesis Example 3. A polyvinyl chloride-based graft copolymer P-2c containing the repeating unit described below was obtained.

Synthesis of Resin P-3c Poly containing the repeating unit described below in the same manner as in Synthesis Example 3 except that 4-methoxyphenyl methacrylate was used in place of 4-hydroxyphenyl methacrylate (HPMA) for Synthesis Example 3. A vinyl chloride-based graft copolymer P-3c was obtained.

Synthesis of Resin P-101c For comparison, the method described below is repeated in the same manner as in Synthesis Example 3 except that vinyl acetate (VAc) is used instead of 4-hydroxyphenyl methacrylate (HPMA) for Synthesis Example 3. A polyvinyl chloride-based graft copolymer P-101c containing a unit was obtained.

Synthesis of Resin P-102c For comparison, the method shown below is the same as that of Synthesis Example 3 except that methyl methacrylate (MMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA) for Synthesis Example 3. A polyvinyl chloride-based graft copolymer P-102c containing a repeating unit was obtained.

<Evaluation>
(Evaluation 5) Evaluation of heat resistance of the resin For each resin synthesized above, the mass reduction rate ([M / M ₀ ] × 100) (%) under the atmosphere of air and nitrogen was determined by the same method as in Evaluation 1. It was measured.

"A" is when the mass reduction rate is less than 30% in both the measurement under the air atmosphere and the nitrogen atmosphere, and the mass loss rate is 30% or more in one or both measurements under the air atmosphere and the nitrogen atmosphere. The case was set to "B". The results are shown in Table 4.

(Evaluation 6) Evaluation of ability to suppress thermal deterioration of additives 1 g of each polyvinyl chloride-based graft copolymer was dissolved in 10 g of a solution of toluene: cyclohexanone = 7: 3 (mass ratio) to prepare a polymer solution. The above formula (1) having a hindered amine-based light stabilizer (trade name: Tinubin 123, manufactured by BASF Japan Ltd.) or tris (pentafluoroethyl) trifluorophosphate (FAP) as a counter anion in this polymer solution. ) Was mixed with 0.01 g of a cyanine dye having the structure shown in) to obtain a resin solution. The above resin solution was applied onto a glass substrate using spin coating, heated on a hot plate set at 200 ° C. for 10 minutes and dried to form a coating film having a thickness of 1 μm.

The glass substrate on which the coating film was formed was heated at 250 ° C. for 10 minutes, and the residual ratio of the additive in the coating film was measured. A glass substrate was ^{cut into a size of 1 cm 2} , immersed in 1.5 mL of acetone, and extracted in an ultrasonic cleaner for 60 minutes. Addition into glass substrate extract by ultra-high performance liquid chromatography / mass spectrometry (UHPLC / MS) (ultra-high performance liquid chromatograph / mass spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System) The agent was quantified. The additive residual ratio ([V ₁ / V ₀ ] × 100) (%) was calculated by dividing the amount of the additive remaining after heating (V ₁ ) by the initial amount of the additive (V _{0) before heating.} The higher the residual ratio of the additive, the better the ability to suppress the thermal deterioration of the additive.

In the measurement of both the resin composition to which the hindered amine-based light stabilizer was added and the resin composition to which the cyanine pigment was added, the case where the residual additive ratio was 80% or more was "A", and in one or both measurements. The case where the residual additive ratio was less than 80% was defined as "B". The results are shown in Table 4.

<Synthesis of resin (group d)>
Synthesis Example 4: Synthesis of Resin P-1d 80 parts by mass of cyclohexanone was prepared as a polymerization solvent. Further, 13 parts by mass of methyl methacrylate (MMA), 4 parts by mass of 2-hydroxyethyl methacrylate (HEMA), and 3 parts by mass of 4-hydroxyphenyl methacrylate (HPMA) were prepared as acrylic monomers. Further, 0.22 parts by mass of benzoyl peroxide (BPO) was prepared as a polymerization initiator. These were placed in a reaction vessel equipped with a stirrer and a reflux tube, and the mixture was stirred and refluxed for 8 hours while being heated to 80 ° C. while introducing nitrogen gas into the reaction vessel. As a result, a polymer solution containing the resin (acrylic copolymer) P-1d described later formed from the repeating unit derived from MMA, the repeating unit derived from HEMA, and the repeating unit derived from HPMA was obtained.

Synthesis of resin P-2d After synthesis example 4, the same method as in synthesis example 4 was used except that N- (4-hydroxyphenyl) methacrylamide (HPMAA) was used instead of 4-hydroxyphenyl methacrylate (HPMA). A polymer solution containing the above resin P-2d was obtained.

Synthesis of Resin P-3d The resin described below was prepared in the same manner as in Synthesis Example 4 except that 4-hydroxyphenylmaleimide (4-HPhMI) was used instead of 4-hydroxyphenylmethacrylate (HPMA) for Synthesis Example 4. A polymer solution containing P-3d was obtained.

Synthesis of Resin P-4d The resin described below was prepared in the same manner as in Synthesis Example 4 except that 3-hydroxyphenylmaleimide (3-HPhMI) was used instead of 4-hydroxyphenylmethacrylate (HPMA) for Synthesis Example 4. A polymer solution containing P-4d was obtained.

Synthesis of Resin P-5d Resin P-, which will be described later, is the same as in Synthesis Example 4 except that 4-methoxyphenyl methacrylate (MPhMA) is used instead of 4-hydroxyphenyl methacrylate (HPMA) for Synthesis Example 4. A polymer solution containing 5d was obtained.

Synthesis of Resin P-6d Similar to Synthesis Example 4 except that 2,6-di-tert-butylphenyl methacrylate (t-BuPhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA). By the method, a polymer solution containing the resin P-6d described later was obtained.

Synthesis of Resin P-7d Synthesis Example 4 except that 2,6-di-tert-butyl-4-methoxyphenyl methacrylate (t-BuMPhMA) was used instead of 4-hydroxyphenyl methacrylate (HPMA). A polymer solution containing the resin P-7d described later was obtained in the same manner as in 4.

Synthesis of Resin P-101d For comparison, the resin P- A polymer solution containing 101d was obtained.

Synthesis of Resin P-102d For comparison, the method described below is the same as in Synthesis Example 4 except that N-phenylmethacrylamide (PhMAA) was used instead of 4-hydroxyphenylmethacrylate (HPMA). A polymer solution containing the resin P-102d of the above was obtained.

Synthesis of Resin P-103d For comparison, the same method as in Synthesis Example 4 is shown below except that N-phenylmaleimide (PhMI) was used instead of 4-hydroxyphenylmethacrylate (HPMA) for Synthesis Example 4. A polymer solution containing the resin P-103d was obtained.

<Making a decorative sheet>
100 parts by mass of transparent homopolypropylene resin (Prime PP; manufactured by Prime Polymer Co., Ltd.), 0.5 parts by mass of tinubin 326 (manufactured by BASF Japan Ltd.) as an ultraviolet absorber, and tinubin 622 (BASF) as a light stabilizer. A resin composition was obtained by adding 0.4 parts by mass of (manufactured by Japan Co., Ltd.) and 0.1 parts by mass of Chimassorb 2020 (manufactured by BASF Japan Ltd.). This resin composition was melt-extruded to obtain a polypropylene resin film having a thickness of 80 μm.

A base material is provided by gravure printing a wood grain pattern using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) on a concealing polyethylene raw fabric (thickness 70 μm) and providing a pattern layer (thickness 3 μm). Got A laminate of the film was obtained by dry-laminating the polypropylene resin film on this substrate via a dry-laminating adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.) (thickness 2 μm).

A polymer solution containing each of the resins (acrylic copolymers) obtained above is applied onto the polypropylene resin film of the laminate so as to have a layer thickness of 8 μm using a bar coater, and the surface is dried. A protective layer was formed and a decorative sheet was obtained. Here, as the polymer solution for the surface protective layer, four kinds of polymer solutions were prepared and used for each resin. That is, the polymer solution itself containing the resin obtained above and xylylene diisocyanate (XDI) (trade name: Takenate (registered trademark) 500; manufactured by Mitsui Kagaku Co., Ltd.) are used as curing agents in terms of solid content mass ratio. Resin: For each of the polymer solutions added so that the curing agent is 7: 3, a hindered amine-based light stabilizer (trade name: Chinubin 123; manufactured by BASF Japan Co., Ltd.) is added or not added as an additive. We prepared 4 kinds.

<Evaluation>
(Evaluation 7) Evaluation of heat resistance of the surface protective layer The mass reduction rate (%) of the surface protective layer in the atmospheric atmosphere was measured by the following method. A differential thermogravimetric simultaneous measuring device (STA7000, manufactured by Hitachi High-Tech Science Co., Ltd.) was used to measure the mass reduction rate (%). A 5 mg surface protective layer was scraped from the decorative sheet obtained above and placed in an aluminum pan to prepare a measurement sample. The sample was heated for 20 minutes at 250 ° C. in an air atmosphere, the initial initial mass before heating weight loss obtained by subtracting the mass _{(M 1)} after heating from _{(M 0) (M = M} 0 -M 1) The mass reduction rate ([M / M ₀ ] × 100) (%) was calculated by dividing by the mass (W _0). The lower the mass reduction rate, the better the heat resistance.

The case where the mass reduction rate was less than 20% was designated as "A", and the case where the mass reduction rate was 20% or more was designated as "B". The results are shown in Table 5.

(Evaluation 8) Evaluation of ability to suppress thermal deterioration of additives The ^{sample prepared by cutting out 1 cm 2} of the decorative sheet obtained above and heating it at 250 ° C. for 20 minutes in the air atmosphere is immersed in 1.5 mL of acetone and ultrasonically. Extraction was performed in a washing machine for 60 minutes. Ultrafast Liquid Chromatography / Mass Spectrometry (UHPLC / MS) (Ultra High Performance Liquid Chromatography / Mass Spectrometer (UHPLC / MS), Agilent 1260 LC System / 6130B Single Quad MS System) in the extract of the cosmetic sheet. The additive was quantified.
Further, the above-mentioned film laminate having no surface protective layer formed was prepared, ^{cut into 1 cm 2 in} the same manner as described above, and subjected to the same heat treatment and extraction operation as described above, in the extract of the film laminate. The amount of additives was quantified.
The amount of the additive in the surface protective layer of the decorative sheet was quantified by taking the difference between the amount of the additive in the extract of the decorative sheet and the amount of the additive in the extract of the film laminate.

The additive residual ratio ([V ₁ / V ₀ ] × 100) (%) was calculated by dividing the amount of the additive remaining after heating (V ₁ ) by the initial amount of the additive (V _{0) before heating.} The higher the residual ratio of the additive, the better the ability to suppress the thermal deterioration of the additive. When the residual additive ratio was 90% or more, it was designated as "A", and when it was less than 90%, it was designated as "B". The results are shown in Table 5.

The present invention is not limited to the above embodiment, and can be variously modified at the implementation stage without departing from the gist thereof. In addition, each embodiment may be carried out in combination as appropriate, in which case the combined effect can be obtained. Further, the above-described embodiment includes various inventions, and various inventions can be extracted by a combination selected from a plurality of disclosed constituent requirements. For example, even if some constituent elements are deleted from all the constituent elements shown in the embodiment, if the problem can be solved and the effect is obtained, the configuration in which the constituent elements are deleted can be extracted as an invention.

Claims (7)

A resin composition containing a resin containing a repeating unit having a partial structure represented by the following general formula (I) or (II) and an additive, and the compounding ratio of the additive to the resin is 50% by mass or less. thing.

In formula (I), Q _A represents the ester bond shown in the formula, _RA represents a substituent, n1 represents an integer of 1-5, and * represents the binding site with the rest of the repeating unit. , ** represent the binding site with the phenyl group in the formula.

Wherein (II), _{Q B} represents a linking group or a single bond other than an ester bond represented by _{Q A} in the formula (I), _{R B} represents a substituent, n2 is an integer of 1 to 5 , * Represent the binding site with the rest of the repeating unit. Provided that at least one of _{R B} represents a hydroxyl group. The resin composition according to claim 1, wherein the content of the repeating unit in the resin is 2 mol% or more and 50 mol% or less with respect to all the repeating units in the resin. The repeating unit according to claim 1 or 2, wherein the repeating unit is one of a repeating unit derived from a (meth) acrylate-based monomer, a repeating unit derived from a (meth) acrylamide-based monomer, and a repeating unit derived from an N-substituted maleimide-based monomer. The resin composition described. In addition to the repeating unit, the resin has a (meth) acrylate-based repeating unit having a linear or branched alkyl group having 1 to 5 carbon atoms in the side chain, and / or a hydroxyl group other than the phenolic hydroxyl group in the side chain. The resin composition according to any one of claims 1 to 3, further containing a (meth) acrylate-based repeating unit. The resin composition according to any one of claims 1 to 3, wherein the resin further contains an olefin-based repeating unit in addition to the repeating unit. The resin composition according to any one of claims 1 to 3, wherein the resin further contains a halogen atom-containing repeating unit in addition to the repeating unit. A film containing the resin composition according to any one of claims 1 to 6.