JP2015120807A - Substrate for hot stamp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate for hot stamp comprising a polylactic acid resin composition, a thermal transfer method and a hot stamp manufacturing method using the substrate, and a material for hot stamp including the substrate.SOLUTION: The substrate for hot stamp comprises the polylactic acid resin composition which contains a polylactic acid resin and a plasticizer containing an ester compound having a (poly)oxyalkylene group or a C2-C6 alkylene group. The content of the plasticizer is 1-25 pts.mass based on 100 pts.mass of the polylactic acid resin. The thermal transfer method and the hot stamp manufacturing method use the substrate. The material for hot stamp includes the substrate.

Description

  The present invention relates to a base material for hot stamping comprising a polylactic acid resin composition, a thermal transfer method using the base material, a method for producing a hot stamp, and a material for hot stamping including the base material.

  Polylactic acid resin is inexpensive because L-lactic acid as a raw material is produced by fermentation using sugar extracted from corn, straw, etc., and the carbon dioxide emission is extremely low because the raw material is derived from plants. In addition, due to the characteristics of the resin such as high rigidity and high transparency, its use is currently expected.

  In Patent Document 1, as a biodegradable card base material that can replace a card base material made of a polyvinyl chloride resin that has been conventionally used, 50 to 90% by weight of a lactic acid-containing polymer, glycols, and an aliphatic dicarboxylic acid On the both sides of the core layer (A) composed of a composition comprising 50 to 10% by weight of a high molecular weight aliphatic polyester obtained by dehydrating polycondensation and adding a coupling agent. Overlay layer (B) comprising 95% by weight and a composition comprising, as an essential component, 50 to 5% by weight of a high molecular weight polyester obtained by dehydrating polycondensation of glycols and aliphatic dicarboxylic acid and adding a coupling agent A biodegradable card base material obtained by laminating is disclosed. The card base material can be used as a card base material for a proof card by printing a face photograph or individual information, etc., and images and prints on the surface of the base material can be performed by thermal transfer using a hot stamp. It is disclosed.

  Patent Document 2 discloses a dehydration weight of a copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate, 82 to 27% by weight, polylactic acid 9 to 40% by weight, a glycol component and an aliphatic dicarboxylic acid. On both surfaces of the core layer (A) composed of a composition comprising 9 to 33% by weight of a high molecular weight aliphatic polyester obtained by condensation as an essential component, 99 to 67% by weight of polylactic acid, a glycol component and an aliphatic dicarboxylic acid A biodegradable card base material is disclosed, in which an overlay layer (B) made of a composition containing as an essential component 1 to 33% by weight of a high-molecular-weight aliphatic polyester obtained by dehydration polycondensation is prepared. The substrate can also be thermally transferred using a hot stamp.

JP-A-11-105224 JP-A-10-157041

  However, the base materials of Patent Documents 1 and 2 cannot be said to have sufficient adhesiveness for hot stamping, and a biodegradable base material having excellent adhesiveness is desired.

  The present invention relates to a base material for hot stamping comprising a polylactic acid resin composition, a thermal transfer method using the base material, a method for producing a hot stamp, and a material for hot stamping including the base material.

The present invention relates to the following [1] to [4].
[1] containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. A base material for hot stamping comprising a polylactic acid resin composition in an amount of 1 to 25 parts by mass.
[2] A polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. A thermal transfer method in which a hot stamp foil having a metal foil layer and an acrylic resin adhesive layer is transferred to a polylactic acid resin composition having 1 to 25 parts by mass using heat.
[3] A polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. Hot stamp foil having a metal foil layer and an acrylic resin adhesive layer is laminated on a base material for a hot stamp made of a polylactic acid resin composition of 1 to 25 parts by weight, and transferred using heat to produce a hot stamp Method.
[4] A polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. A hot stamping material comprising a hot stamping base material comprising a polylactic acid resin composition of 1 to 25 parts by mass, and a hot stamping foil having a metal foil layer and an acrylic resin adhesive layer.

  The base material for hot stamps of the present invention is excellent in the adhesion durability of hot stamps that have been thermally transferred, and has the excellent effect of being able to suppress bleeding of the contained components.

  The base material for hot stamping of the present invention contains a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms. It consists of the polylactic acid resin composition which is 1-25 mass parts with respect to 100 mass parts of lactic acid resin.

  Regarding the factor that the base material for hot stamping of the present invention has improved the adhesive durability of hot stamping (also simply referred to as durability), polylactic acid is added by adding a plasticizer having a specific structure to the polylactic acid resin. The mobility of the resin is efficiently increased, and the degree of entanglement between the polylactic acid molecules and the polymer molecules of the adhesive layer is improved at the interface between the polylactic acid resin molded product and the adhesive layer of the hot stamp, and the physical and chemical interactions are improved. It is considered that the action has increased, leading to an improvement in storage stability over time. Moreover, since the affinity between the plasticizer and the polylactic acid resin is high, it is presumed that the dispersibility in the polylactic acid resin is enhanced, and that bleeding is excellent.

[Polylactic acid resin composition]
The polylactic acid resin composition in the present invention contains a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms. Hereinafter, each component will be described.

[Polylactic acid resin]
Examples of the polylactic acid resin include commercially available polylactic acid resins (for example, manufactured by Nature Works, trade names: Nature Works PLA / NW3001D, NW4032D, etc.), and polylactic acid resins synthesized from lactic acid and lactide according to a known method. Can be mentioned. From the viewpoint of improvement in strength and heat resistance, a polylactic acid resin having an optical purity of preferably 90% or more, more preferably 95% or more is preferable. For example, a polylactic acid resin having a relatively high molecular weight and a high optical purity is manufactured by Nature Works. Lactic acid resin (NW4032D etc.) is preferable. The optical purity is a ratio of mol% occupied by L-form or D-form in polylactic acid resin.

  Moreover, in this invention, other biodegradable resin other than the said polylactic acid resin may be mix | blended suitably in the range which does not impair the effect of this invention. Examples of other biodegradable resins include polyester resins such as polybutylene succinate, polyhydroxyalkanoic acid, and the like. Further, a part or all of the polylactic acid resin may be blended as a polymer alloy by blending the other biodegradable resin or non-biodegradable resin such as polypropylene and polylactic acid resin. In the present specification, “biodegradable” means a property that can be decomposed into a low molecular weight compound by a microorganism in nature. Specifically, JIS K6953 (ISO 14855) “controlled aerobic composting conditions”. This means biodegradability based on the “Aerobic and Ultimate Biodegradation and Disintegration Test”.

  The content of the polylactic acid resin in the polylactic acid resin composition is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and still more preferably from the viewpoint of the rigidity of the molded body. From the viewpoint of blending a plasticizer or the like and improving durability, it is preferably 99% by mass or less, more preferably 98% by mass or less, and further preferably 95% by mass or less.

[Plasticizer]
As the plasticizer in the present invention, those containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms are used from the viewpoint of durability and bleed resistance. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group. The oxyalkylene group preferably has 2 to 4 carbon atoms, preferably an oxyethylene group, an oxypropylene group or an oxybutylene group, and more preferably an oxyethylene group or an oxypropylene group.

  As an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, a (poly) oxyalkylene group or 2 to 6 carbon atoms, preferably carbon is present in the molecule. Although it will not specifically limit if it has a C2-C4 alkylene group, Preferably, from a durable and bleed-resistant viewpoint, a (poly) oxyalkylene group or C2-C6, Preferably C2-C2 1 type, or 2 or more types selected from the group consisting of polyester plasticizers, polyhydric alcohol ester plasticizers, polycarboxylic acid ester plasticizers, and phosphate ester plasticizers having 4 alkylene groups be able to.

  Specific examples of the polyester plasticizer are preferably dicarboxylic acids having an alkylene group having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and preferably 2 to 6 carbon atoms, more preferably 2 carbon atoms. Examples thereof include polyesters based on dialcohols having -4 alkylene groups or their (poly) oxyalkylene adducts. Examples of the dicarboxylic acid include succinic acid, adipic acid, sebacic acid, terephthalic acid, and isophthalic acid. Examples of the dialcohol include propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, and triethylene glycol. Moreover, the hydroxyl group and carboxy group of the polyester terminal may be esterified with monocarboxylic acid or monoalcohol and blocked.

  The number average molecular weight of the polyester-based plasticizer is preferably 300 to 1500, more preferably 300 to 1000, from the viewpoints of bleed resistance, durability, and volatile resistance. In the present specification, the number average molecular weight of the polyester plasticizer can be calculated according to the method described in Examples described later.

  Specific examples of the polyhydric alcohol ester plasticizer are preferably polyhydric alcohols having an alkylene group having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, or (poly) oxyalkylene adducts or polyalkylenes thereof. Examples thereof include mono-, di- and triesters of a glycol with a monocarboxylic acid having preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Examples of the polyhydric alcohol include propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, dialcohols such as ethylene glycol, diethylene glycol, and triethylene glycol, and glycerin. it can. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Examples of the monocarboxylic acid include acetic acid and propionic acid. When the polyhydric alcohol has an alkylene group having 2 to 6 carbon atoms, the polyhydric alcohol may or may not be a (poly) oxyalkylene adduct. When the polyhydric alcohol does not have an alkylene group having 2 to 6 carbon atoms, a (poly) oxyalkylene adduct is used as the polyhydric alcohol.

  The polyvalent carboxylic acid ester plasticizer is preferably a polyvalent carboxylic acid having an alkylene group having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and preferably 1 to 12 carbon atoms, more preferably carbon. Examples thereof include mono-, di- and triesters with a mono-alcohol having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms or a (poly) oxyalkylene adduct thereof. Examples of the polyvalent carboxylic acid include succinic acid and adipic acid. Examples of the monoalcohol include methanol, ethanol, 1-propanol, and 1-butanol. Specific examples of the polyvalent carboxylic acid ester plasticizer include, for example, an average addition mole number of dicarboxylic acid such as succinic acid, adipic acid, citric acid, sebacic acid and phthalic acid, trimellitic acid and the like and ethylene oxide. And esters with polyethylene glycol monomethyl ether of 3 to 3 (addition of 2 to 3 mol of ethylene oxide per hydroxyl group). In the case where the polyvalent carboxylic acid has an alkylene group having 2 to 6 carbon atoms, the monovalent alcohol may or may not be a (poly) oxyalkylene adduct. When the polyvalent carboxylic acid does not have an alkylene group having 2 to 6 carbon atoms, a (poly) oxyalkylene adduct is used as the monovalent alcohol.

  Examples of the phosphoric ester plasticizer include mono-, di- or triesters of phosphoric acid and (poly) oxyalkylene adducts of the above monoalcohols. Specific examples include tris (ethoxyethoxyethyl) phosphate.

Moreover, as said compound, specifically, 1 type, or 2 or more types chosen from the group which consists of the following compound groups (A)-(C) is preferable, and when using in combination of 2 or more types, the same compound Different groups or different compound groups may be used.
Compound group (A) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 0 to 2 alkylene oxides per hydroxyl group. Ester compound group (B) which is alcohol added by 5 to 5 mol Formula (I):
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.
Compound group (C) represented by formula (II):

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms. X, y and z are each independently a positive number indicating the average number of moles added of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less)
Compound represented by

Compound group (A)
The ester compound contained in the compound group (A) is an ester compound having two or more ester groups in the molecule, and at least one alcohol component constituting the ester compound has 2 carbon atoms per hydroxyl group. A compound which is an alcohol obtained by adding (or having) an average of 0.5 to 5 moles of alkylene oxide is preferably a polyhydric alcohol ester or a polycarboxylic acid ether ester having two or more ester groups in the molecule. An ester compound in which at least one of the alcohol components constituting the ester compound is an alcohol obtained by adding an average of 0.5 to 5 moles of alkylene oxide having 2 to 3 carbon atoms per hydroxyl group is more preferable.

  Specific compounds include an ester of acetic acid and glycerin ethylene oxide average 3 to 6 mol adduct (addition of 1 to 2 mol of ethylene oxide per hydroxyl group), an average addition mol number of acetic acid and ethylene oxide of 4 to 4 6 Esters with polyethylene glycol, Esters with polyethylene glycol monomethyl ether having an average addition mole number of succinic acid and ethylene oxide of 2 to 3 (addition of 2 to 3 mol of ethylene oxide per hydroxyl group), Adipic acid and diethylene glycol monomethyl Esters with ethers and esters with 1,3,6-hexanetricarboxylic acid and diethylene glycol monomethyl ether are preferred.

The average molecular weight of the ester compound contained in the compound group (A) is preferably 250 or more, more preferably 300 or more, still more preferably 350 or more, and still more preferably, from the viewpoint of durability, bleed resistance, and volatile resistance. It is 400 or more, preferably 700 or less, more preferably 600 or less, further preferably 550 or less, and further preferably 500 or less. The average molecular weight can be obtained by calculating the saponification value by the method described in JIS K0070 and calculating from the following formula.
Average molecular weight = 56108 × (number of ester groups) / saponification value

Compound group (B)
R ¹ in formula (I) represents an alkyl group having 1 to 4 carbon atoms, and two of them exist in one molecule and exist at both ends of the molecule. R ¹ may be linear or branched as long as it has 1 to 4 carbon atoms. As carbon number of an alkyl group, 1-4 are preferable from a durable and bleed-resistant viewpoint, and 1-2 are more preferable. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an iso-butyl group. Among them, a methyl group and an ethyl group are preferable, Groups are more preferred.

R ² in formula (I) represents an alkylene group having 2 to 4 carbon atoms, and a linear alkylene group is a preferred example. Specific examples include an ethylene group, a 1,3-propylene group, and a 1,4-butylene group, and from the viewpoint of durability and bleed resistance, an ethylene group, a 1,3-propylene group, and a 1,4-butylene group. Group is preferred, and ethylene group is more preferred. However, all R ² may be the same or different.

R ³ in Formula (I) represents an alkylene group having 2 to 6 carbon atoms, and OR ³ is present in the repeating unit as an oxyalkylene group. R ³ may be linear or branched as long as it has 2 to 6 carbon atoms. As carbon number of an alkylene group, 2-6 are preferable from a viewpoint of durability and bleed resistance, and 2-3 are more preferable. Specifically, ethylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,3-butylene group, 1,4-butylene group, 2-methyl-1,3 -Propylene group, 1,2-pentylene group, 1,4-pentylene group, 1,5-pentylene group, 2,2-dimethyl-1,3-propylene group, 1,2-hexylene group, 1,5-hexylene Group, 1,6-hexylene group, 2,5-hexylene group, 3-methyl-1,5-pentylene group, among which ethylene group, 1,2-propylene group, 1,3-propylene group are preferable. However, all R ³ may be the same or different.

  m represents the average number of repeating oxyalkylene groups. From the viewpoint of durability and bleed resistance, the number is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.

  n represents the average number of repeating units (average degree of polymerization), and is a number from 1 to 12. From the viewpoint of durability and bleed resistance, n is preferably a number of 1 to 12, more preferably 1 to 6, and even more preferably 1 to 5. The average degree of polymerization may be determined by analysis such as NMR, but can be calculated according to the method described in Examples below.

Specific examples of the compound represented by formula (I) include: R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1,3-propylene group , M is a number from 1 to 4, and n is a number from 1 to 6, R ¹ is all methyl group, R ² is ethylene group or 1,4-butylene group, R ³ is ethylene group or 1, A compound which is a 3-propylene group and m is a number of 1 to 3 and n is a number of 1 to 5 is more preferable.

The compound represented by the formula (I) is not particularly limited as long as it has the above structure, but those obtained using the following raw materials (1) to (3) are preferable. In addition, (1) and (2) or (2) and (3) may form an ester compound. (2) may be an acid anhydride or an acid halide.
(1) Monohydric alcohol having an alkyl group having 1 to 4 carbon atoms
(2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms
(3) Dihydric alcohol having an alkylene group having 2 to 6 carbon atoms

(1) A monohydric alcohol having an alkyl group having 1 to 4 carbon atoms The monohydric alcohol having an alkyl group having 1 to 4 carbon atoms is an alcohol containing R ¹ , specifically, methanol, Examples include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 1,1-dimethyl-1-ethanol. Among these, from the viewpoint of durability and bleed resistance, methanol, ethanol, 1-propanol, and 1-butanol are preferable, methanol and ethanol are more preferable, and methanol is more preferable.

(2) Dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms The dicarboxylic acid having an alkylene group having 2 to 4 carbon atoms is a dicarboxylic acid containing R ² , specifically, succinic acid, Examples include glutaric acid, adipic acid, and derivatives thereof such as succinic anhydride, glutaric anhydride, dimethyl succinate, dibutyl succinate, dimethyl glutarate, dimethyl adipate, and the like. Among these, from the viewpoint of durability and bleed resistance, succinic acid, adipic acid and derivatives thereof, for example, succinic anhydride, dimethyl succinate, dibutyl succinate, dimethyl adipate are preferable, succinic acid and derivatives thereof, For example, succinic anhydride, dimethyl succinate, and dibutyl succinate are more preferable.

(3) Dihydric alcohol having an alkylene group having 2 to 6 carbon atoms The dihydric alcohol having an alkylene group having 2 to 6 carbon atoms is a dihydric alcohol containing R ³ , specifically, Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,5-hexanediol, Examples include 1,6-hexanediol and 3-methyl-1,5-pentanediol. Of these, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and 1,4-butanediol are preferable from the viewpoint of durability and bleed resistance, and diethylene glycol and triethylene are preferred. Glycol, 1,2-propanediol, and 1,3-propanediol are more preferable, and diethylene glycol, triethylene glycol, and 1,3-propanediol are more preferable.

Therefore, as said (1)-(3),
(1) The monohydric alcohol is one or more selected from the group consisting of methanol, ethanol, 1-propanol, and 1-butanol, and (2) the dicarboxylic acid is succinic acid, adipic acid, glutaric acid, and 1 or 2 or more types selected from the group consisting of these derivatives, (3) dihydric alcohol is diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, tetraethylene glycol, and It is preferably one or more selected from the group consisting of 1,4-butanediol,
(1) The monohydric alcohol is one or more selected from the group consisting of methanol and ethanol, and (2) the dicarboxylic acid is selected from the group consisting of succinic acid, adipic acid, and derivatives thereof, or 2 or more, and (3) the dihydric alcohol is one or more selected from the group consisting of diethylene glycol, triethylene glycol, 1,2-propanediol, and 1,3-propanediol. Preferably
(1) The monohydric alcohol is methanol, (2) the dicarboxylic acid is one or more selected from the group consisting of succinic acid and derivatives thereof, and (3) the dihydric alcohol is diethylene glycol, triethylene glycol, And one or more selected from the group consisting of 1,3-propanediol.

Although there is no limitation in particular as a method of obtaining the ester compound represented by Formula (I) using said (1)-(3), For example, the method of the following aspect 1 and aspect 2 is mentioned.
Aspect 1: (2) Step of synthesizing dicarboxylic acid ester by performing esterification reaction of (2) dicarboxylic acid with (1) monohydric alcohol, and (3) Step of esterifying reaction of obtained dicarboxylic acid ester with dihydric alcohol A method comprising the steps of: (1) monohydric alcohol, (2) dicarboxylic acid, and (3) dihydric alcohol reacting together

  Among these, the method of Embodiment 1 is preferable from the viewpoint of adjusting the average degree of polymerization. In addition, reaction of each above-mentioned process can be performed in accordance with a well-known method.

  The compound represented by the formula (I) preferably has an acid value of 1.50 mgKOH / g or less, more preferably 1.00 mgKOH / g or less, and a hydroxyl value of from the viewpoint of bleed resistance and durability. From the viewpoint of bleed resistance and durability, it is preferably 10.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less, still more preferably 3.0 mgKOH / g or less. In addition, in this specification, the acid value and hydroxyl value of a plasticizer can be measured according to the method as described in the below-mentioned Example.

  Moreover, the number average molecular weight of the compound represented by the formula (I) is preferably 300 to 1500, and more preferably 300 to 1000, from the viewpoints of bleed resistance, durability, and volatile resistance. In the present specification, the number average molecular weight of the plasticizer can be calculated according to the method described in Examples described later.

  The saponification value of the compound represented by formula (I) is preferably from 500 to 800 mgKOH / g, more preferably from 550 to 750 mgKOH / g, from the viewpoint of bleed resistance and durability. In addition, in this specification, the saponification value of a plasticizer can be measured according to the method as described in the below-mentioned Example.

  From the viewpoint of bleed resistance and durability, the compound represented by the formula (I) preferably has an alkyl esterification rate (terminal alkyl esterification rate) with respect to two molecular ends of 95% or more, more preferably 98. % Or more. In the present specification, the terminal alkyl esterification rate of the plasticizer can be calculated according to the method described in Examples described later.

  The ether group value of the compound represented by the formula (I) is preferably 0 to 8 mmol / g, more preferably 0 to 6 mmol / g, from the viewpoints of bleed resistance and durability. In the present specification, the ether group value of the plasticizer can be calculated according to the method described in Examples described later.

Compound group (C)
The compound represented by the formula (II) is a polyether-type phosphate triester, which may be a symmetric structure or an asymmetric structure. However, from the viewpoint of ease of production, a symmetric structure phosphate triester is preferable.

R ⁴ , R ⁵ , and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and may be linear or branched. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group, and an ethyl group, a propyl group, and a butyl group are preferable. Further, from the viewpoints of bleed resistance and durability, an alkyl group having 2 to 3 carbon atoms, that is, an ethyl group and a propyl group are more preferable.

A ¹ , A ² , and A ³ each independently represent an alkylene group having 2 or 3 carbon atoms, and may be linear or branched. Specific examples include an ethylene group, an n-propylene group, and an isopropylene group. Among these, an ethylene group is preferable from the viewpoint of bleed resistance and durability. A ¹ , A ² , and A ³ form an oxyalkylene group (alkylene oxide) with an adjacent oxygen atom to form a repeating structure in the compound represented by the formula (II).

  x, y, and z are each independently a positive number indicating the average added mole number of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less. Among these, from the viewpoint of bleed resistance, x, y, and z are positive numbers, and x + y + z is preferably a number that exceeds 3 and less than 12, and a number that exceeds 4 and less than 12 is preferable. A number that satisfies 6 or more and 9 or less is more preferable.

Therefore, as the compound represented by the formula (II),
(1) R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represent an alkylene group having 2 or 3 carbon atoms. , X, y, and z are each independently a positive number indicating the average number of added moles of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less,
(2) R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, A ¹ , A ² and A ³ are all ethylene groups, and x, y and z are positive. And more preferably a compound in which x + y + z is more than 4 and less than 12;
(3) R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms, A ¹ , A ² and A ³ are all ethylene groups, and x, y and z are positive. And a compound satisfying x + y + z of 6 or more and 9 or less is more preferable.

Specific examples of the compound represented by the formula (II) include tris (ethoxyethoxyethyl) phosphate [in the formula (II), R ⁴ , R ⁵ and R ⁶ are all ethyl groups, A ¹ , A ² , A ³ is an ethylene group, x, y and z are all 2; in addition to x + y + z = 6], tris (methoxyethoxyethyl) phosphate (x + y + z = 6), tris (propoxyethoxyethyl) phosphate (x + y + z = 6) ), Tris (butoxyethoxyethyl) phosphate (x + y + z = 6), tris (methoxyethoxyethoxyethyl) phosphate (x + y + z = 9), tris (ethoxyethoxyethoxyethyl) phosphate (x + y + z = 9), tris (propoxyethoxyethoxyethyl) Symmetric polyether type such as phosphate (x + y + z = 9) Phosphoric acid triester, bis (ethoxyethoxyethyl) methoxyethoxyethoxyethyl phosphate (x + y + z = 7), bis (methoxyethoxyethoxyethyl) ethoxyethoxyethyl phosphate (x + y + z = 8), bis (ethoxyethoxyethyl) {butoxyethoxyethyl} Phosphoric acid so that an asymmetric polyether-type phosphate triester such as phosphate (x + y + z = 6), or a polyoxyethylene adduct or a mixture of polyoxypropylene adducts of alcohols having 1 to 4 carbon atoms satisfies formula (II) Triesterified asymmetric polyether-type phosphate ester may be mentioned. From the viewpoint of bleed resistance and durability, tris (ethoxyethoxyethyl) phosphate, tris (propoxyethoxyethyl) phosphate, tris ( Butoxyethyl ethoxyethoxyethyl) phosphate, tris (propoxyethoxy ethoxyethyl) phosphate is preferred, tris (ethoxyethoxyethyl) phosphate is more preferable.

  Content of ester compound having (poly) oxyalkylene group or C2-C6 alkylene group in plasticizer, preferably polyester system having (poly) oxyalkylene group or C2-C6 alkylene group One or more contents selected from the group consisting of a plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer, more preferably the compound group ( The content of one or more compounds selected from the group consisting of A) to (C) is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of bleed resistance and durability. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, More preferably, it is substantially 100 mass%. In the present specification, the content of the plasticizer means the total content when a plurality of compounds are contained.

  The content of the plasticizer is 1 part by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 8 parts by mass or more from the viewpoint of durability with respect to 100 parts by mass of the polylactic acid resin. More preferably, it is 10 parts by mass or more, and still more preferably 15 parts by mass or more. Moreover, from a viewpoint of bleed resistance and durability, it is 25 mass parts or less, Preferably it is 23 mass parts or less, More preferably, it is 20 mass parts or less.

  The content in the polylactic acid resin composition is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 8% by mass or more, and still more preferably 10% by mass or more, from the viewpoint of durability. It is. Moreover, from a viewpoint of bleed resistance and durability, Preferably it is 20 mass% or less, More preferably, it is 18 mass% or less, More preferably, it is 17 mass% or less.

[Organic crystal nucleating agent]
The polylactic acid resin composition in the present invention preferably contains an organic crystal nucleating agent from the viewpoint of improving the crystallization speed of the polylactic acid resin, improving the crystallinity of the polylactic acid resin, and improving the durability. .

As the organic crystal nucleating agent in the present invention, it is preferable to use one or more organic crystal nucleating agents selected from the group consisting of the following (a) to (d).
(A) From the group consisting of a compound having an isoindolinone skeleton, a compound having a diketopyrrolopyrrole skeleton, a compound having a benzimidazolone skeleton, a compound having an indigo skeleton, a compound having a phthalocyanine skeleton, and a compound having a porphyrin skeleton One or more organic compounds selected [referred to as organic crystal nucleating agent (a)]
(B) One or more organic compounds selected from the group consisting of carbohydrazides, uracils, and N-substituted ureas (referred to as organic crystal nucleating agent (b))
(C) One kind selected from the group consisting of metal salts of dialkyl aromatic sulfonates, metal salts of phosphoric acid esters, metal salts of phenylphosphonic acid, metal salts of rosin acids, aromatic carboxylic acid amides, and rosin acid amides Or two or more organic compounds [referred to as organic crystal nucleating agent (c)]
(D) One or more organic compounds selected from the group consisting of a compound having a hydroxyl group and an amide group in the molecule and a hydroxy fatty acid ester [referred to as organic crystal nucleating agent (d)]

  Among these, from the viewpoint of durability, the organic crystal nucleating agent (c) and the organic crystal nucleating agent (d) are preferable.

As the organic crystal nucleating agent (c), from the above viewpoint, a phenylphosphonic acid metal salt having an optionally substituted phenyl group and a phosphonic group (—PO (OH) ₂ ) is preferable. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms in an alkoxy group, and the like. Specific examples of phenylphosphonic acid include unsubstituted phenylphosphonic acid, methylphenylphosphonic acid, ethylphenylphosphonic acid, propylphenylphosphonic acid, butylphenylphosphonic acid, dimethoxycarbonylphenylphosphonic acid, and diethoxycarbonylphenylphosphonic acid. And unsubstituted phenylphosphonic acid is preferred.

  Examples of the metal salt of phenylphosphonic acid include salts of lithium, sodium, magnesium, aluminum, potassium, calcium, barium, copper, zinc, iron, cobalt, nickel, and the like, and zinc salts are preferable.

  From the above viewpoint, the compound having a hydroxyl group and an amide group in the molecule of the organic crystal nucleating agent (d) is preferably an aliphatic amide having a hydroxyl group, having two or more hydroxyl groups in the molecule, and having two amide groups. An aliphatic amide having two or more is more preferable. Specific examples include hydroxy fatty acid monoamides such as 12-hydroxy stearic acid monoethanolamide, methylene bis 12-hydroxy stearic acid amide, ethylene bis 12-hydroxy stearic acid amide, hexamethylene bis 12-hydroxy stearic acid amide and the like. Etc.

  Moreover, as the hydroxy fatty acid ester of the organic crystal nucleating agent (d), a hydroxy fatty acid ester having 12 to 22 carbon atoms of the fatty acid is preferable, and hydroxy having two or more hydroxyl groups and two or more ester groups in the molecule. Fatty acid esters are more preferred. Specific examples include 12-hydroxystearic acid triglyceride, 12-hydroxystearic acid diglyceride, 12-hydroxystearic acid monoglyceride, pentaerythritol mono-12-hydroxystearate, pentaerythritol di-12-hydroxystearate, pentaerythritol. -Hydroxy fatty acid esters such as tri-12-hydroxystearate.

  These may be used alone or in combination of two or more thereof, and among these, one or more selected from the group consisting of hydroxy fatty acid bisamide and metal salt of phenylphosphonic acid is preferable from the viewpoint of durability. More preferred are ethylenebis12-hydroxystearic acid amide and metal salts of unsubstituted phenylphosphonic acid.

  Further, the mass ratio of the hydroxy fatty acid bisamide and the metal salt of phenylphosphonic acid (hydroxy fatty acid bisamide / phenylphosphonic acid metal salt) is preferably 0.2 or more, more preferably 0.3 or more, from the viewpoint of durability. More preferably, it is 0.5 or more, and from the same viewpoint, it is preferably 6 or less, more preferably 4 or less, and further preferably 2 or less.

  From the viewpoint of durability, the content of the organic crystal nucleating agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more with respect to 100 parts by mass of the polylactic acid resin. Preferably, 2 parts by mass or more is more preferable, and 3 parts by mass or more is even more preferable. Further, from the same viewpoint, 10 parts by mass or less is preferable, 7 parts by mass or less is more preferable, and 5 parts by mass or less is more preferable. In the present specification, the content of the organic crystal nucleating agent means the total content of all the organic crystal nucleating agents contained in the polylactic acid resin composition.

[Hydrolysis inhibitor]
In addition, from the viewpoint of durability, the polylactic acid resin composition in the present invention may further contain a hydrolysis inhibitor in addition to the above components.

  Examples of the hydrolysis inhibitor include carbodiimide compounds such as polycarbodiimide compounds and monocarbodiimide compounds. That is, it is preferable that the polylactic acid resin composition in the present invention further contains a carbodiimide compound in addition to the above components. In the present invention, an aromatic carbodiimide compound is preferable from the viewpoint of durability, and a monocarbodiimide compound is preferable from the viewpoint of fluidity during molding. Therefore, an aromatic monocarbodiimide compound is preferable from the viewpoint of achieving both durability and fluidity during molding.

  Examples of the polycarbodiimide compound include poly (4,4′-diphenylmethanecarbodiimide), poly (4,4′-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, poly (1,3,3). 5-triisopropylbenzene and 1,3-diisopropylbenzene) polycarbodiimide. Examples of the monocarbodiimide compound include N, N′-di-2,6-diisopropylphenylcarbodiimide.

  You may use the said carbodiimide compound individually or in combination of 2 or more types. Poly (4,4′-dicyclohexylmethane carbodiimide) is obtained from carbodilite LA-1 (manufactured by Nisshinbo Chemical Co., Ltd.), poly (1,3,5-triisopropylbenzene) polycarbodiimide and poly (1,3,5-tri (Isopropylbenzene and 1,3-diisopropylbenzene) polycarbodiimide is Stavaxol P and Stavaxol P-100 (manufactured by Rhein Chemie), N, N'-di-2,6-diisopropylphenylcarbodiimide is BioAdidede 100 (Rhein Chemie) ) Can be purchased and used separately.

  From the viewpoint of durability, the content of the hydrolysis inhibitor is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass with respect to 100 parts by mass of the polylactic acid resin. It is above, Preferably it is 7 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less.

  The polylactic acid resin composition in the present invention is a filler (inorganic filler, organic filler), a flame retardant, an antioxidant, a hydrocarbon wax, or an anionic surfactant as components other than those described above. Lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments other than metallic pigments, antifungal agents, antibacterial agents, foaming agents, and the like can be contained within a range that does not impair the effects of the present invention. . Moreover, it is also possible to contain other polymer materials and other resin compositions as long as the effects of the present invention are not impaired. In addition, these content is not specifically limited, According to a well-known technique, it can set suitably.

  The polylactic acid resin composition in the present invention contains a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms. If it will be 1-25 mass parts with respect to 100 mass parts of lactic acid resin, it can prepare without limitation. For example, a plasticizer containing a polylactic acid resin, an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and a raw material containing various components as necessary, a sealed kneader, uniaxial or biaxial Can be prepared by melt kneading using a known kneader such as an extruder or an open roll kneader. After the melt-kneading, the melt-kneaded product may be dried or cooled according to a known method. In addition, the raw materials can be subjected to melt kneading after being uniformly mixed in advance using a Henschel mixer, a super mixer, or the like. In order to promote the plasticity of the polylactic acid resin during melt kneading, it may be melt-mixed in the presence of a supercritical gas.

  From the viewpoint of improving the moldability and prevention of deterioration of the polylactic acid resin composition, the melt kneading temperature is preferably 160 ° C or higher, more preferably 165 ° C or higher, further preferably 170 ° C or higher, and preferably 250 ° C or lower. More preferably, it is 230 degrees C or less, More preferably, it is 200 degrees C or less. The melt-kneading time cannot be generally determined depending on the melt-kneading temperature and the type of the kneader, but is preferably 15 to 900 seconds.

  Since the polylactic acid resin composition thus obtained has good processability (moldability), it is molded into a base material for hot stamping.

[Base material for hot stamping]
The base material for hot stamping of the present invention is not particularly limited as long as the polylactic acid resin composition is molded. For example, the obtained polylactic acid resin composition can be prepared by extrusion molding, injection molding, or press molding.

  In extrusion molding, for example, a sheet-like resin molded body can be obtained by filling a polylactic acid resin composition in a heated extruder and melting it, followed by extrusion from a T die. Further, the sheet-like resin molded body is immediately brought into contact with a cooling roll, and the sheet is cooled to Tg or less of the resin composition to adjust the crystallinity of the sheet. It is good also as a sheet-like resin molding. In addition, when filling an extruder, the raw material which comprises the polylactic acid resin composition in this invention, for example, the ester compound which has a polylactic acid resin and a (poly) oxyalkylene group or a C2-C6 alkylene group is included. A raw material containing a plasticizer and, if necessary, various additives may be filled, melt kneaded, and then extruded.

  The temperature of the extruder is preferably 170 ° C. or higher, more preferably 175 ° C. or higher, and further preferably 180 ° C. or higher, from the viewpoint of uniformly mixing the polylactic acid resin composition and preventing deterioration of the polylactic acid resin. The temperature is preferably 240 ° C. or lower, more preferably 220 ° C. or lower, and still more preferably 210 ° C. or lower. The temperature of the cooling roll is preferably 40 ° C. or lower, more preferably 30 ° C. or lower, and even more preferably 10 ° C. or lower from the viewpoint of adjusting the crystallinity of the polylactic acid resin composition.

  The extrusion speed is preferably 0.5 m / min or more, more preferably 1 m / min or more, further preferably 2 m / min or more, preferably 200 m / min, from the viewpoint of adjusting the crystallinity of the polylactic acid resin composition. Min or less, more preferably 150 m / min or less, and even more preferably 100 m / min or less.

  In injection molding, for example, the polylactic acid resin composition of the present invention can be filled into a mold having a desired shape and molded using an injection molding machine.

  As an injection molding machine, for example, a machine having a cylinder and a screw inserted through the cylinder as main components [J110AD-180H (manufactured by Nippon Steel Works), etc.] can be used. In addition, when filling the injection molding machine, a raw material constituting the polylactic acid resin composition in the present invention, for example, an ester compound having a polylactic acid resin and a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms. However, in the present invention, from the viewpoint of dispersibility of plasticizers, crystal nucleating agents, etc., those previously melt-kneaded may be used. It is preferable to fill the injection molding machine.

  The set temperature of the cylinder is preferably 180 ° C. or higher from the viewpoint of impact resistance, and is preferably 220 ° C. or lower, more preferably 210 ° C. or lower from the viewpoint of suppressing deterioration of the polylactic acid resin.

  The mold temperature is preferably 110 ° C. or less, more preferably 90 ° C. or less, and still more preferably 80 ° C. or less from the viewpoint of improving the crystallization speed and improving workability. Moreover, 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 60 degreeC or more is further more preferable.

  Although the holding time in a metal mold | die is not specifically limited, From a viewpoint of the productivity of the molded object which consists of a polylactic acid resin composition, 3-90 second is preferable, for example in a 80-90 degreeC metal mold, 10-80 Seconds are more preferred.

  In press molding, for example, the polylactic acid resin composition in the present invention can be enclosed by a frame having a sheet shape, and can be prepared by press molding.

  The press molding temperature and pressure are, for example, preferably 170 ° C. or higher and 240 ° C. or lower, 5 MPa [abs] or higher and 30 MPa [abs] or lower, more preferably 175 ° C. or higher and 220 ° C. or lower. Temperature of 10 MPa [abs] or more and 25 MPa [abs] or less, more preferably 180 ° C. or more and 210 ° C. or less, pressure of 10 MPa [abs] or more and 20 MPa [abs] or less. Can be pressed. Although the press time cannot be generally determined by the temperature and pressure of the press, it is preferably 1 minute or longer, preferably 10 minutes or shorter, more preferably 7 minutes or shorter, and even more preferably 5 minutes or shorter.

  In addition, immediately after pressing under the above conditions, the temperature is preferably 0 ° C. or higher and 40 ° C. or lower, and the pressure is 0.1 MPa [abs] or higher and 30 MPa [abs] or lower, more preferably 10 ° C. or higher and 30 ° C. or lower. Temperature, 0.2 MPa [abs] or more and 20 MPa [abs] or less, more preferably 10 ° C. or more and 20 ° C. or less, 0.3 MPa [abs] or more and 10 MPa [abs] or less It is preferable to press and cool under these conditions. In order to adjust the crystallinity by cooling the polylactic acid resin composition in the present invention below its Tg by pressing under this temperature condition, the pressing time cannot be determined unconditionally depending on the temperature and pressure of the press, Preferably it is 1 minute or more, preferably 10 minutes or less, more preferably 7 minutes or less, and even more preferably 5 minutes or less. After the above cooling, the crystallinity of the resin can be adjusted by maintaining the temperature at the glass transition point or higher and the melting point or lower of the resin composition.

  Examples of the obtained base material for hot stamping include parts for home appliance casings having a thickness of about 1 to 3 mm obtained by injection molding, interior parts and decorative parts for automobiles, various emblems and design covers. Moreover, a clear case, a clear file, a magnetic card, a prepaid card, etc. with a thickness of about 0.1 to 1 mm obtained by extrusion molding can be mentioned. Examples include a blister pack having a thickness of about 0.1 to 1 mm obtained by press molding and thermoforming, a decorative part for automobiles, a decorative part for home appliances, and the like.

  The base material for stamps of the present invention is excellent in adhesion durability of hot-transferred hot stamps and can suppress bleeding of components contained therein, so that a hot stamp excellent in durability can be provided.

〔Hot Stamp〕
The hot stamp of the present invention is not particularly limited as long as the hot stamp base material of the present invention is used. For example, it can be prepared by laminating a hot stamp foil (also referred to as a transfer foil) on the hot stamp base material of the present invention and transferring it by hot pressing.

[Hot stamp foil]
As an aspect of the hot stamp foil, a metal foil layer and an adhesive layer are essential components, but 1) a base film layer, 2) a release layer, 3) a protective layer, 4) a metal foil layer, and 5) an adhesive layer. It is preferably composed of five basic layers. Moreover, when it has the said 5 layers, it is preferable to have 2) a mold release layer, 3) a protective layer, 4) a metal foil layer, and 5) an adhesive layer in this order on the base film layer.

1) Base film layer There is no restriction | limiting in particular as a base film layer, Any can be used if it is used for the normal hot stamp foil which has sufficient self-holding property. Specifically, polyester-based resins, polyamide resins, polyamide-imide resins, polyethylene resins, polypropylene resins, cellulose acetate resins, polycarbonate resins, polyvinyl chloride resins, and other resin-based films, cellophane paper, glassine paper, and other paper and Japanese paper A sheet or sheet can be used. The thickness of the base film layer is preferably 6 μm or more, more preferably 10 μm or more, preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 20 μm or less.

2) Release layer As the release layer, paraffin wax, silicone, acrylic resin, urethane resin, fiber resin, melamine resin, urea resin, urea-melamine resin, benzoguanamine resin or the like alone or these Examples of the coating film include a mixture as a main component. These are formed by, for example, applying to the base film layer and drying after application. The thickness of the release layer is preferably 0.01 μm or more, more preferably 0.015 μm or more, preferably 2 μm or less, more preferably 1 μm or less, and even more preferably 0.1 μm or less.

3) Protective layer As the protective layer, a thermoplastic resin, a thermosetting resin, an ultraviolet curable resin, or an electron beam curable resin is used. Specific examples include polyester resins, epoxy resins, melamine resins, and acrylic resins. For example, these resins are dissolved in an organic solvent, applied to the surface of the release layer, and dried after application. The thickness of the protective layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. Pigments and dyes may be added to this protective layer from the viewpoint of design, and include inorganic pigments such as carbon black, iron oxide, and titanium oxide, and organic pigments such as phthalocyanine-based, quinacridone-based, and azo-based pigments. . Various dispersants may be used to improve the dispersibility of the pigment.

4) Metal foil layer The metal foil layer is formed by forming a metal such as aluminum, tin, copper, or chromium by, for example, vacuum deposition on the protective layer, and aluminum is preferable. The thickness of the metal foil layer is preferably 0.01 μm or more, more preferably 0.02 μm or more, preferably 0.3 μm or less, more preferably 0.1 μm or less, and even more preferably 0.05 μm or less. Note that the metal layer is not limited to one layer, and a metal foil layer having a thickness within the above range may be formed by laminating two or more layers. When two or more layers are laminated, the type of metal is the same. Or different.

5) Adhesive layer The adhesive layer is formed by layering an adhesive, and examples of the adhesive include emulsion-type or organic solvent-type resins from the viewpoint of adhesiveness with a polylactic acid resin. Among them, from the viewpoint of adhesiveness and durability with the hot stamp base material of the present invention, an acrylic emulsion type is used as an adhesive containing an acrylic resin (also referred to as an acrylic resin) alone or as a main component. It is preferable to use an adhesive or an acrylic organic solvent adhesive. The content of the acrylic resin in the adhesive is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, and substantially 100% by mass. Further preferred. It should be noted that other resins can be used as long as the effects of the present invention are not impaired, and examples thereof include vinyl acetate, vinyl chloride, polyethylene, and styrene-butadiene. The adhesive layer can be formed by applying an adhesive to, for example, a metal foil layer and drying it after application. The thickness of the adhesive layer is not particularly limited and depends on the surface shape and material of the transfer target, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more, preferably Is 50 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, and more preferably 5 μm or less.

  Examples of the components of the hot stamp foil include hot stamp foils that can be used in the present invention. From the viewpoint of adhesiveness to the hot stamp base material of the present invention and hot stamp durability, acrylic is used as an adhesive layer. Those containing a resin are preferred. Therefore, for example, a hot stamp foil having at least a metal foil layer and an acrylic resin adhesive layer is preferably used.

  The thickness of the hot stamping foil is preferably 5 μm or more, more preferably 10 μm or more, further preferably 13 μm or more from the viewpoint of hot stamping stability, and preferably 80 μm or less, more preferably from the viewpoint of design. It is 60 μm or less, more preferably 40 μm or less, and further preferably 20 μm or less.

  Specific examples of hot stamping foils that can be used in the present invention include KLX series, SFX series, SH series, SHC series, SLM series, AM series, AP series, AC series, BM series, CR series, manufactured by Kurz Japan. , F-AR series, GLP series, BRP series, B series, M series and the like.

  When the hot stamping foil is laminated on the hot stamping base material, the hot stamping foil may be laminated so that the adhesive layer is in direct contact with the surface of the base material, and a thermal transfer process described later can be performed from the hot stamping foil.

[Thermal transfer method]
The thermal transfer method is not particularly limited, but a thermocompression bonding method (hot pressing method) is preferably used.

  As a device used for thermocompression bonding, any known press molding machine can be used without any particular limitation.

  As conditions for thermocompression bonding, the temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, more preferably 170 ° C. or higher, and preferably 230 ° C. or lower, more preferably 210 ° C. or lower, more preferably 190 ° C. It is below ℃.

  The pressing pressure is preferably 0.05 MPa or more, more preferably 0.1 MPa or more, further preferably 0.2 MPa or more, preferably 5 MPa or less, more preferably 3 MPa or less, and further preferably 1 MPa or less.

  The heating and pressing time is preferably 3 seconds or more, more preferably 5 seconds or more, still more preferably 8 seconds or more, preferably 30 minutes or less, more preferably 10 minutes or less, still more preferably 1 minute or less, More preferably, it is 20 seconds or less.

  As specific heat transfer, for example, when the hot stamp foil is a laminate of a base film layer, a release layer, a protective layer, a metal foil layer, and an adhesive layer in order, the adhesive layer is formed on the surface of the substrate. After laminating so as to be in direct contact, the above-described thermal transfer treatment is performed, and then the base film layer and the release layer are peeled off to prepare a hot stamp.

  Thus, the hot stamp of the present invention is obtained. Since the hot stamp of the present invention is excellent in adhesion durability, parts for home appliance casings having a thickness of about 1 to 3 mm obtained by injection molding particularly requiring durability, interior parts and decorative parts for automobiles, It is suitably used for various emblems and design covers.

[Method of manufacturing hot stamp]
The present invention also provides a method for manufacturing the hot stamp.

  The hot stamp production method is not particularly limited as long as the hot stamp base material of the present invention is used. For example, it contains a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. Manufacturing characterized by laminating a hot stamping foil having a metal foil layer and an acrylic resin adhesive layer on a base material for hot stamping comprising a polylactic acid resin composition of 1 to 25 parts by mass, and transferring it using heat A method is mentioned.

Specifically, for example, a production method including the following steps (1) to (2) may be mentioned.
Step (1): containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 100 parts by mass of the polylactic acid resin. Step (2) of preparing a base material for hot stamping comprising a polylactic acid resin composition in an amount of 1 to 25 parts by weight to the base material for hot stamping obtained in Step (1), a metal foil layer and Laminating a hot stamping foil with an acrylic resin adhesive layer and transferring it using heat

  In step (1), the base material for hot stamping of the present invention is prepared. Specifically, it may be prepared in the same manner as the above-mentioned hot stamp base material.

  In the step (2), a hot stamp foil is laminated on the hot stamp base material obtained in the step (1) so that the adhesive layer is in contact with the surface of the base material, and thermal transfer is performed. As the hot stamping foil, the above-mentioned hot stamping foil can be used similarly, and the laminating method is also as described above. In addition, the above-described conditions can be similarly adopted as the thermal transfer conditions.

[Material for Hot Stamp]
Furthermore, the present invention provides a hot stamping material in which the hot stamping base material and a hot stamping foil are combined. The above-described materials can be used for both the hot stamp base material and the hot stamp foil, and the shape and amount of use can be appropriately set according to the use, application location, application environment, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Acid value, hydroxyl value, and saponification value of plasticizer]
Acid value: Analysis is performed according to the test method of JIS K 0070, except that toluene / ethanol = 2/1 (volume ratio) is used as a titration solvent.
Hydroxyl value: Analysis is performed according to the test method of JIS K 0070, except that acetic anhydride / pyridine = 1/4 (volume ratio) is used as the acetylating reagent and the addition amount is 3 mL.
Saponification value: Analysis is performed according to the test method of JIS K 0070, except that the temperature of the water bath is 95 ° C. and the heating temperature is 1 hour.

[Molecular weight of plasticizer compound group (A)]
The molecular weight of the plasticizer compound group (A) is determined from the saponification value by the following formula.
Average molecular weight = 56108 × (number of ester groups in one molecule) / saponification value

[Molecular weight, terminal alkyl esterification rate, and ether group value of polyester-based plasticizer and plasticizer compound group (B) ester compound]
Molecular weight: In this specification, the molecular weight of the polyester plasticizer and the (B) ester compound means a number average molecular weight, and is calculated from the acid value, hydroxyl value, and saponification value according to the following formula.
Average molecular weight M = (M ₁ + M ₂ −M ₃ × 2) × n + M ₁ − (M ₃ −17.01) × 2 + (M ₃ −17.01) × p + (M ₂ −17.01) × q + 1. 01 × (2-pq)
q = hydroxyl value × M ÷ 56110
2-pq = acid value × M ÷ 56110
Average degree of polymerization n = saponification number × M ÷ (2 × 56110) −1
Terminal alkyl esterification rate: The molecular terminal alkyl esterification rate (terminal alkyl esterification rate) can be calculated from the following formula. The larger the value of the molecular terminal alkyl esterification rate, the free carboxyl group or hydroxyl group There are few, and it shows that the molecular terminal is fully alkylesterified.
Terminal alkyl esterification rate (%) = (p ÷ 2) × 100
However, M ₁ : dicarboxylic acid used as a raw material and monohydric alcohol used as a raw material
Molecular weight of diester M ₂ : Molecular weight of dihydric alcohol used as raw material M ₃ : Molecular weight of monohydric alcohol used as raw material p: Number of terminal alkyl ester groups in one molecule q: Number of terminal hydroxyl groups in one molecule Ether group number : The ether group value which is the number of millimoles (mmol) of the ether group in 1 g of the carboxylic acid ester is calculated from the following formula.
Ether group value (mmol / g) = (m−1) × n × 1000 ÷ M
Where m: average number of repeating oxyalkylene groups (m-1 represents the number of ether groups in one molecule of dihydric alcohol)
In addition, when using multiple types of dicarboxylic acid, monohydric alcohol, and dihydric alcohol, molecular weight uses the molecular weight of a number average value. In the polyester plasticizer, when no monohydric alcohol is used, M ₁ is the molecular weight of the dicarboxylic acid.

<Production Example 1 of Plasticizer> (Diester of Succinic Acid and Triethylene Glycol Monomethyl Ether)
A 3 L flask equipped with a stirrer, thermometer and dehydration tube was charged with 500 g of succinic anhydride, 2463 g of triethylene glycol monomethyl ether, and 9.5 g of paratoluenesulfonic acid monohydroxide, and nitrogen (500 mL / min) was added to the space. While blowing, the reaction was carried out at 110 ° C. for 15 hours under reduced pressure (4 to 10.7 kPa). The acid value of the reaction solution was 1.6 (mgKOH / g). After adding 27 g of adsorbent KYOWARD 500SH (manufactured by Kyowa Chemical Industry Co., Ltd.) to the reaction solution and stirring and filtering at 80 ° C. and 2.7 kPa for 45 minutes, triethylene at a liquid temperature of 115 to 200 ° C. and a pressure of 0.03 kPa. After distilling off the glycol monomethyl ether and cooling to 80 ° C., the residual liquid was filtered under reduced pressure to obtain a diester [(MeEO ₃ ) ₂ SA] of succinic acid and triethylene glycol monomethyl ether as a filtrate. The obtained diester had a weight average molecular weight of 410, a viscosity (23 ° C.) of 27 mPa · s, an acid value of 0.2 mgKOH / g, a saponification value of 274 mgKOH / g, a hydroxyl value of 1 mgKOH / g or less, and a hue APHA200.

<Production Example 2 of Plasticizer> (Diester of succinic acid, 1,3-propanediol and methanol, raw material (molar ratio): dimethyl succinate / 1,3-propanediol (1.5 / 1))
In a four-necked flask (with a stirrer, thermometer, dropping funnel, distillation tube, nitrogen blowing tube), 521 g (6.84 mol) of 1,3-propanediol and 5.9 g of a methanol solution containing 28 mass% sodium methoxide as a catalyst (Sodium methoxide 0.031 mol) was added, and methanol was distilled off with stirring at normal pressure and 120 ° C. for 0.5 hour. Thereafter, 1500 g (10.26 mol) of dimethyl succinate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour, and methanol produced by the reaction was distilled off at normal pressure and 120 ° C. Next, the mixture was cooled to 60 ° C., 5.6 g of 28 mass% sodium methoxide-containing methanol solution (0.029 mol of sodium methoxide) was added, the temperature was raised to 120 ° C. over 2 hours, and then the pressure was applied over 1 hour. The methanol was gradually distilled off from normal pressure to 3.7 kPa. Then, after cooling to 80 ° C., 18 g of KYOWARD 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at a pressure of 4.0 kPa and 80 ° C. for 1 hour, followed by filtration under reduced pressure. The filtrate was raised at a pressure of 0.1 kPa and the temperature was raised from 85 ° C. to 194 ° C. over 2.5 hours to distill off the remaining dimethyl succinate to obtain a room temperature yellow liquid. In addition, the usage-amount of the catalyst was 0.58 mol with respect to 100 mol of dicarboxylic acid ester. (R ¹ in formula (I): methyl, R ² : ethylene, R ³ : 1,3-propylene, m = 1, n = 4.4; acid value 0.64 mgKOH / g; hydroxyl value 1.3 mgKOH / g Saponification number 719.5 mg KOH / g; number average molecular weight 850; terminal alkyl esterification rate 98.5%; ether group number 0 mmol / g.

<Production Example 3 of Plasticizer> (Tris (ethoxyethoxyethyl) phosphate)
To a 1 liter four-necked flask, 600 g (4.47 mol) of diethylene glycol monoethyl ether was added and stirred under reduced pressure (20 kPa) while blowing dry nitrogen gas at a flow rate of 50 mL per minute. Next, 114 g (0.745 mol) of phosphorus oxychloride was slowly added dropwise while maintaining the reaction system at room temperature (15 ° C.), and then aged at 40 to 60 ° C. for 5 hours. Thereafter, 149 g of a 16% by mass aqueous sodium hydroxide solution was added for neutralization, and excess unreacted diethylene glycol monoethyl ether was distilled off under reduced pressure at a temperature of 70 to 120 ° C., and further contacted with steam to obtain crude phosphoric acid. 367 g of triester was obtained. Further, 300 g of a 16% by mass aqueous sodium chloride solution was added to the crude phosphoric acid triester for washing. Thereafter, the phase-separated lower phase was drained, and the remaining upper phase was dehydrated under reduced pressure at 75 ° C., and the solid content was further removed by filtration to obtain 266 g of the desired tris (ethoxyethoxyethyl) phosphate ( Yield 80%). This tris (ethoxyethoxyethyl) phosphate is a colorless and transparent uniform liquid. As a result of the chloro ion analysis, the chloro ion content was 10 mg / kg or less.

Examples 1-10 and Comparative Examples 1-7
The composition raw materials shown in Table 1 are melt-kneaded at 190 ° C. using a directional meshing twin screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM-41SS), strand cut, and pellets of a polylactic acid resin composition Got. In addition, the obtained pellet was dehumidified and dried at 110 ° C. for 2 hours, and the water content was adjusted to 500 ppm or less.

  The obtained pellets were injection molded using an injection molding machine (Japan Steel Works, J110AD-180H) with a cylinder temperature of 200 ° C. Examples 1 to 10 had a mold temperature of 80 ° C and a molding time of 60 seconds. A flat test piece (100 mm × 100 mm × 2 mm) was obtained. Further, since the crystallization speed of the comparative example is slower than that of the example, the comparative example 1 has a mold temperature of 110 ° C. and a molding time of 120 seconds, and the comparative examples 2 to 7 have a mold temperature of 80 ° C. and a molding time of 120. A flat plate test piece (100 mm × 100 mm × 2 mm) was obtained in seconds.

  Hot stamping was performed using a press molding machine (Lab Press Press P2-30T manufactured by Toyo Seiki Seisakusho). A hot stamp foil (AM4153-601AL manufactured by Kurz Japan Co., Ltd.) was cut to a size of 20 mm × 20 mm, and the hot stamp foil cut out on the lithographic test piece obtained above was placed between the lower part of the press and the lithographic test piece. Inserted a 1 mm thick Teflon (registered trademark) sheet, pressed at a temperature of 180 ° C. and a pressing pressure of 0.4 MPa for 10 seconds, and hot stamped from above. In addition, after cooling to room temperature, the release layer and the base film layer were peeled from the test piece after hot stamping.

The configuration of the hot stamping foil used in this test was as follows.
1) Base film layer: polyethylene terephthalate film, thickness 12 μm
2) Release layer: silicone resin release agent, thickness 0.02 μm
3) Protection (colored layer): polymethyl methacrylate resin, thickness 1 μm
4) Metal foil layer: Aluminum, thickness 0.04 μm
5) Adhesive layer: acrylic emulsion-type adhesive, thickness 2 μm

The raw materials in Table 1 are as follows.
<Polylactic acid resin>
NW4032D: Polylactic acid resin, “Nature Works 4032D” manufactured by Nature Works
<Plasticizer>
(MeEO ₃ ) ₂ SA: Diester of succinic acid and triethylene glycol monomethyl ether produced in Production Example 1 of the plasticizer DAIFATTY-101: “DAIFATTY-101” manufactured by Daihachi Chemical Industry Co., Ltd., adipic acid and diethylene glycol monomethyl Diester MeSA-1,3PD with ether / benzyl alcohol (= 1/1) mixture: Diester of succinic acid, 1,3-propanediol and methanol produced in Production Example 2 of the plasticizer TEP-2: Plasticizer Tris (ethoxyethoxyethyl) phosphate DOA produced in Production Example 3 of bis (2-ethylhexyl) adipate, “DOA” manufactured by Daihachi Chemical Co., Ltd.
DOP: Bis (2-ethylhexyl) phthalate, “Vinizer 85” manufactured by Kao Corporation
BOL: Isobutyl oleate, “Vini Sizer 30” manufactured by Kao Corporation
TOTM: Tris (n-octyl, decyl mixture) trimellitate, "Trimex N-08" manufactured by Kao Corporation
ESO: Epoxidized soybean oil, “Kapox S-6” manufactured by Kao Corporation
<Organic crystal nucleating agent>
OHC18EB: Ethylene bis 12-hydroxystearic acid amide, “Sripacks H” manufactured by Nippon Kasei Co., Ltd.
PPA-Zn: unsubstituted phenylphosphonic acid zinc salt, “Eco Promote” manufactured by Nissan Chemical Industries, Ltd.
<Hydrolysis inhibitor>
Monocarbodiimide: Diisopropylphenylcarbodiimide, “BioAdide 100” manufactured by Rhein Chemie
<Inorganic materials>
Talc: “MICRO ACE P-6” manufactured by Nippon Talc
Glass fiber: “CSF3PE-941HS 3 mm chopped strand” manufactured by Nitto Boseki Co., Ltd.

  The characteristics of the obtained base material for hot stamping and the hot stamping material were evaluated according to the methods of Test Examples 1 and 2 below. The results are shown in Table 1.

Test Example 1 <Hot Stamp Durability>
The hot stamped test piece (100 mm × 100 mm × 2 mm)] is stored in a constant temperature room at a temperature of 60 ° C./85% humidity, taken out with time, and left in a constant temperature room at a temperature of 23 ° C./humidity of 50%. did. The appearance of the hot stamp and the Sellotape (registered trademark) peel test were carried out, and the maximum storage time during which the appearance of the hot stamp did not change and the Sellotape (registered trademark) did not peel was regarded as the hot stamp durability. The storage time is preferably 200 hours or longer, more preferably 300 hours or longer.

Test Example 2 <Evaluation of bleed resistance>
Using a test piece (100 mm × 100 mm × 2 mm) before hot stamping, the sample was allowed to stand in a temperature-controlled room at a temperature of 60 ° C./humidity of 85% for 1 week, and then visually checked for additive bleed on the surface appearance. The bleed resistance was evaluated according to the following criteria. The smaller the bleed, the better the bleed resistance, preferably B or more, and more preferably A.

[Criteria for bleed resistance]
A: It cannot be visually confirmed, and no liquid or powder adheres even if it is traced with a finger.
B: Although it cannot be confirmed visually, there is a slight liquid or powder adhesion to the finger when traced with the finger.
C: Liquid droplets or powder is visually confirmed on the surface of the molded body, and liquid or powder adheres to the finger when traced with the finger.

  From Table 1, when hot stamping foil is heat-sealed to the hot stamping base material of the present invention, Comparative Example 1 using no plasticizer is compared with Examples 2, 5, 8 and Comparative Examples 1 and 2. Although it does not bleed, it is inferior in durability, and Comparative Example 2 in which the amount of plasticizer is 30 parts by mass is also inferior in bleed resistance and durability. By using an appropriate amount of plasticizer, bleed resistance, It can be seen that the durability is also excellent. Moreover, it turns out that it is excellent only in the case where a specific plasticizer is used by the comparison of Example 1, 5, 9, 10 and Comparative Examples 3-7 that it is excellent in bleed resistance and durability. From Examples 3-5, it turns out that the direction which promoted crystallization by using 2 types of crystal nucleating agents together is excellent in durability. From the comparison between Examples 5 and 6, it can be seen that the use of the hydrolysis inhibitor is superior in durability.

  The base material for hot stamping of the present invention is a component for home appliance casings having a thickness of about 1 to 3 mm obtained by injection molding that requires durability, interior parts and decorative parts for automobiles, various emblems and design covers. It can be suitably used as a hot stamp product.

Claims (7)

  Containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 1 to 100 parts by mass of the polylactic acid resin. A base material for hot stamping comprising a polylactic acid resin composition of 25 parts by mass.   The plasticizer has a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, a polyester plasticizer, a polyhydric alcohol ester plasticizer, a polycarboxylic acid ester plasticizer, and a phosphate ester plasticizer. The base material of Claim 1 containing the 1 type (s) or 2 or more types chosen from the group which consists of an agent. Plasticizer
(A) An ester compound having two or more ester groups in the molecule, wherein at least one of the alcohol components constituting the ester compound is an average of 0.5 to 3 alkylene oxides per hydroxyl group An ester compound which is an alcohol added with 5 mol
(B) Formula (I):
R ¹ O—CO—R ² —CO — [(OR ³ ) _m O—CO—R ² —CO—] _n OR ¹ (I)
Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is an alkylene group having 2 to 4 carbon atoms, R ³ is an alkylene group having 2 to 6 carbon atoms, and m is 1 to 6 And n represents a number from 1 to 12, provided that all R ² may be the same or different, and all R ³ may be the same or different.
And a compound represented by formula (II):

(In the formula, R ⁴ , R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 4 carbon atoms, and A ¹ , A ² and A ³ each independently represents an alkylene group having 2 or 3 carbon atoms. X, y and z are each independently a positive number indicating the average number of moles added of the oxyalkylene group, and x + y + z is a number exceeding 3 and satisfying 12 or less)
The base material of Claim 1 or 2 containing the 1 type (s) or 2 or more types chosen from the group which consists of a compound represented by these.   Furthermore, the base material in any one of Claims 1-3 which consists of a polylactic acid resin composition containing a carbodiimide compound.   Containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 1 to 100 parts by mass of the polylactic acid resin. A thermal transfer method in which a hot stamp foil having a metal foil layer and an acrylic resin adhesive layer is transferred to a polylactic acid resin composition of 25 parts by mass using heat.   Containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 1 to 100 parts by mass of the polylactic acid resin. A method for producing a hot stamp, comprising laminating a hot stamping foil having a metal foil layer and an acrylic resin adhesive layer on a hot stamping base material composed of 25 parts by mass of a polylactic acid resin composition, and transferring the laminate using heat.   Containing a polylactic acid resin and a plasticizer containing an ester compound having a (poly) oxyalkylene group or an alkylene group having 2 to 6 carbon atoms, and the content of the plasticizer is 1 to 100 parts by mass of the polylactic acid resin. A hot stamping material comprising a hot stamping base material comprising a polylactic acid resin composition of 25 parts by mass, and a hot stamping foil having a metal foil layer and an acrylic resin adhesive layer.