KR20200012725A - Modifier for resin sheet for molded article, resin sheet for resin molded article and resin molded article - Google Patents

Abstract

Provided are a modifier for a resin sheet, a resin sheet, and a resin molded body, exhibiting high temperature antifogging properties, high temperature antifogging persistence, and activity in a good balance. The modifier for a resin sheet includes following components A and B, wherein component A/component B = 10 / 90 to 75 / 25 (mass ratio). The component A is one or more selected from the group of polyglycerin fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkyl ether, and polyalkylene glycol. The component B is one or more selected from fatty acid alkali metal salts having 8 to 22 carbon atoms.

Description

Modifier for resin sheet, resin sheet for resin molded body and resin molded body for molding into a molded body {MODIFIER FOR RESIN SHEET FOR MOLDED ARTICLE, RESIN SHEET FOR RESIN MOLDED ARTICLE AND RESIN MOLDED ARTICLE}

The present invention relates to a modifier for a resin sheet for molding into a molded article having antifogging property, a resin sheet for an antifogging resin molded article, and an antifogging resin molded article.

Since resin molded bodies widely used including food containers are hydrophobic, they are easily clouded by moisture in the contents. Originally, a resin molded article was intended to protect a product, but recently, it has become important to be able to visually recognize the contents without clouding, and in particular, the demand for antifogging property is increasing in food containers. Especially, when the contents are warm foods, the persistence of the antifogging property at the time of being packed for a long time in a refrigerator after being packed at high temperature is strongly demanded.

Conventionally, as a method of providing antifogging property to a resin sheet, the method of apply | coating a polyglycerol fatty acid ester (for example, refer patent document 1), and apply | coating the specific vinyl copolymer and higher fatty acid salt which have a nitrogen-containing organic group in a side chain Method (for example, refer to Patent Document 2), method for applying polyglycerin fatty acid ester and sucrose fatty acid ester, dimethylpolysiloxane (for example, refer to Patent Document 3), and to apply polyglycerol fatty acid ester and sucrose fatty acid ester, silicone oil The method (for example, refer patent document 4) is known.

Japanese Patent Laid-Open No. 11-300904 Japanese Patent Publication No. 2004-244605 Japanese Patent Publication No. 2012-036259 Japanese Patent Laid-Open No. 11-277688

However, the resin molded body is provided in a process of packing the contents in a state where the molded bodies overlap with each other after being molded, and prevents the overlapped resin molded bodies from being picked up in a close contact with each other in the molding step and the packing step, one by one. Excellent activity is also required at the same time for the purpose of making it easy to fall off the molded body.

The antifogging resin sheet proposed conventionally could not exhibit high temperature antifogging property and high temperature antifog persistence which lasted for a long time, and activity in good balance.

An object of the present invention is to provide a modifier for a resin sheet, a resin sheet for a resin molded article, and a resin molded article for molding into a molded article exhibiting a good balance of high temperature antifogging property, high temperature antifogging persistence, and activity.

This invention contains following component A, component B, and component C, Component A / component B = 29 / 71-63 / 37 (mass ratio), (component A + component B) / component C = 40 / 60-70 The modifier for resin sheets for shape | molding to the molded object which is / 30 (mass ratio) is related.

Component A: at least one selected from glycerin or a condensate of glycerin (condensation degree 2 to 10) and esters of fatty acids having 8 to 24 carbon atoms;

Component B: one or more selected from fatty acid sodium salts having 8 to 18 carbon atoms;

Component C: 90-40 mass% of structural units 2 formed from 10-60 mass% of structural units 1 formed from the vinyl monomer represented by following General formula (1), and other vinyl monomers copolymerizable with the vinyl monomer represented by General formula (1) 100 mass%),

As the structural unit 2,

10-40 mass% of structural units formed from the hydroxyalkyl (meth) acrylate which has a C1-C4 hydroxyalkyl group,

10-70 mass% of structural units formed from the alkyl (meth) acrylate which has a C1-C4 alkyl group have respectively on the conditions which become 100 mass% in total with the said structural unit 1, respectively.

Vinyl copolymer of number average molecular weight 20000 ~ 90000

In Chemical Formula 1,

R ¹ : a hydrogen atom or a methyl group;

R ² : alkylene group having 1 to 4 carbon atoms;

R ³ and R ⁴ : an alkyl group having 1 to 4 carbon atoms

As fatty acids, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, sorbic acid, enanthic acid, caprylic acid, pelagonic acid, capric acid, undecylic acid, undecylenic acid, lauric acid, tridecyl acid, Myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, henoxylic acid, behenic acid, tricosyl acid, lignoseric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 12-hydric Hydroxystearic acid, ricinoleic acid, and the like. The fatty acid provided to component A of this invention is a C8-C24 fatty acid. Specifically, caprylic acid, pelagonic acid, capric acid, undecyl acid, undecylenic acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, Arachidic acid, henoxylic acid, behenic acid, tricosyl acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 12-hydroxystearic acid, ricinoleic acid, and the like.

As the fatty acid provided in the component A of the present invention, a fatty acid having 8 to 18 carbon atoms is more preferable.

Component A may have a hydroxyl group of at least 1 glass in the molecule | numerator of partial ester.

For example,

(1) As a condensate of glycerin (condensation degree 2-10) and a partial ester of fatty acid,

Partial esters of diglycerin with caprylic acid, lauric acid, stearic acid, or oleic acid,

Partial esters of tetraglycerin and lauric acid,

Partial esters of hexaglycerin and stearic acid,

And partial esters of decaglycerol with lauric acid, palmitic acid or stearic acid.

(2) as partial esters of glycerin and fatty acids,

And partial esters of glycerin, caprylic acid, lauric acid, stearic acid and oleic acid.

As the fatty acid metal salt, sodium caprylate salt, lithium caprylate salt, sodium laurate salt, potassium palmitate salt, sodium palmitate salt, sodium oleate salt, sodium stearate salt, potassium isostearate salt, Hehenic acid potassium salt etc. are mentioned.

The component B provided in this invention is a C8-18 fatty acid sodium salt, A sodium caprylate salt, a sodium laurate salt, a sodium palmitoleate salt, a sodium oleate salt, a sodium stearate salt, etc. are mentioned. .

The component C provided in this invention is 90-60 mass% of the structural unit 1 formed from the vinyl monomer represented by following General formula (1), and 90 the structural unit 2 formed from the other vinyl monomer copolymerizable with the vinyl monomer represented by General formula (1). I have it in ratio of -40 mass% (100 mass% in total),

As the structural unit 2,

10-40 mass% of structural units formed from the hydroxyalkyl (meth) acrylate which has a C1-C4 hydroxyalkyl group,

10-70 mass% of structural units formed from the alkyl (meth) acrylate which has a C1-C4 alkyl group have respectively on the conditions which become 100 mass% in total with the said structural unit 1, respectively.

It is a vinyl copolymer of the number average molecular weights 20000-90000.

A number average molecular weight can be measured by a well-known method using GPC (gel permeation chromatography).

[Formula 1]

In Chemical Formula 1,

R ¹ : a hydrogen atom or a methyl group;

R <^2> : C1-C4 alkylene groups, such as a methylene group, ethylene group, trimethylene group, and tetramethylene group;

R <^3> , R <^4> : C1-C4 alkyl groups, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, and an isobutyl group

Component C can be synthesized by a known method. For example, the structural unit 1 and the structural unit 2 are dissolved in a solvent such as methanol, and a radical polymerization initiator and a radical chain transfer agent are appropriately added, and then synthesized by performing a radical polymerization reaction at a radical polymerization temperature under a nitrogen atmosphere. Can be.

Although various well-known types can be used for the structural unit 2 which comprises component C, Alkyl (meth) acryl which has a hydroxyalkyl (meth) acrylate which has a C1-C4 hydroxyalkyl group, and a C1-C4 alkyl group One or two or more selected from the rates are preferred.

As hydroxyalkyl (meth) acrylate which has a C1-C4 hydroxyalkyl group,

Hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxy Propyl methacrylate, 4-hydroxybutyl methacrylate, 2,2-dihydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 4,4-dihydroxybutyl acrylate, 2,2 -Dihydroxyethyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4,4-dihydroxybutyl methacrylate, etc. are mentioned.

Especially, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferable.

Examples of the alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate and butyl methacrylate. The rate etc. are mentioned.

Especially, ethyl acrylate and methyl methacrylate are preferable.

The modifier for resin sheets of this invention contains component A, component B, and component C, Component A / component B = 29 / 71-63 / 37 (mass ratio), (component A + component B) / component C = 40 / It is 60-70 / 30 (mass ratio).

It is preferable to make ratio of the component A, the component B, and the component C into (component A + component B) / component C = 48 / 52-64 / 36 (mass ratio).

In this invention, a well-known thing can be used as a resin sheet for resin moldings which apply | coats the modifier for resin sheets. For example,

1) polystyrene resin sheet composed of polystyrene, styrene acrylonitrile copolymer,

2) polyester-based resin sheet composed of polyethylene terephthalate, polylactic acid, etc. composed of ethylene glycol terephthalic acid copolymer, etc.

3) polyvinyl chloride-based resin sheet composed of polyvinyl chloride, ethylene-vinyl chloride copolymer,

4) acrylic resin sheet composed of polymethyl methacrylate, methyl methacrylate / styrene copolymer,

5) polyamide-based resin sheet composed of 6-nylon, 6,6-nylon, etc.

6) polycarbonate resin sheet,

7) Polyolefin resin sheet etc. which consist of polyethylene, a polypropylene, etc. are mentioned.

The resin sheet for resin moldings of the present invention,

It is preferable that it is polystyrene type, polyester type, or polyolefin type.

What is necessary is just to shape | mold the resin sheet for resin moldings by a well-known method, and an amorphous sheet, an unstretched sheet, a simultaneous biaxial stretching sheet, a sequential biaxial stretching sheet, etc. are mentioned.

In addition, these resin sheets for resin moldings may be subjected to surface treatment such as corona treatment. Although there is no restriction | limiting in particular in corona treatment degree, It is preferable to process so that it may become 35mN / m-70mN / m.

A well-known method can be used as a method of apply | coating the modifier for resin sheets of this invention to a resin sheet. For example, the method of apply | coating the coating liquid prepared by melt | dissolving the resin sheet modifier in the solvent by the spray coat method, the gravure coat method, the air knife coat method, the bar coat method, the kiss coat method, the flow coat method, the dip coat method, etc. Can be mentioned. As a solvent, water, alcohol, toluene, ethyl acetate, etc. can be used individually or in mixture. Especially, it is preferable to use water or the liquid mixture of water and C1-C3 alcohol.

After apply | coating the modifier for resin sheets, drying is normally performed at 60-120 degreeC.

As the resin sheet for resin moldings of the present invention,

It is preferable that the modifier for resin sheets is apply | coated to the surface at 5-200 mg / m <^2> .

However, the coating amount is not limited to these.

In addition to the modifier for resin sheets, mold release agents, such as a silicone oil and a polyalkylene polymer, can also be apply | coated to the resin sheet for resin molded objects of this invention as needed. You may apply such a mold release agent to the modifier coating surface for resin sheets, or an opposite surface. When apply | coating such a mold release agent to the modifier coating surface for resin sheets, you may mix previously with the modifier for resin sheets, and may apply separately.

This invention includes the resin molded object shape | molded using the resin sheet for resin molded objects mentioned above.

The resin molded body may be thermoformed according to the use to form a container or the like. Examples of the thermoforming method include vacuum molding and pressure molding. Examples of the resin molded article include lids and trays for containers for beverages and foods.

This invention demonstrated above has the effect which can provide the resin sheet for resin molded objects excellent in high temperature antifog property, high temperature antifog persistence, and activity.

EXAMPLE

EXAMPLES Hereinafter, although an Example is illustrated in order to make the structure and effect of this invention more concrete, this invention is not limited to these Examples. In addition, in the following Example, the reference example, and a comparative example, a part means a mass part and% means the mass%.

<Test division 1 (production of resin sheet for resin molding)>

Example 1:

0.28 g of partial esters of decaglycerin and lauric acid (A-1), 0.68 g of sodium oleate (B-1), and 1.04 g of vinyl copolymer (C-1) were converted into water / isopropyl alcohol = 90/10 (mass ratio). It melt | dissolved in 98.0 g of the solvents, and prepared the coating liquid of 2% of effective concentration.

After apply | coating the adjusted coating liquid to 10 g / m <^2> with the bar coater, it apply | coated to the polyethylene terephthalate resin sheet (microcrystal type | mold, surface treatment with wet tension of 46 mN / m by corona treatment), and dried at 70 degreeC The resin sheet for resin moldings was produced.

In the same manner as in Example 1, the resin sheets for resin moldings of Examples 2 to 4, Reference Examples 5 to 16, and Comparative Examples 1 to 7 were produced. Table 1 summarizes the contents thereof, including Example 1.

<Test division 2 (evaluation of resin sheet for resin molding)>

The high temperature antifogging property, high temperature antifogging persistence, and activity were evaluated by the following method about the resin sheet for resin moldings created by test section 1. The results are summarized in Table 1.

Evaluation method of high temperature antifogging property:

The resin sheet for resin molded articles obtained in the test section 1 was placed in a beaker containing hot water at 80 ° C. so that the coated surface of the modifier for resin sheets became the inner surface of the beaker, and was left to stand in an atmosphere at 5 ° C. for 1 hour. The degree of adhesion of water droplets to the water was evaluated by the following evaluation criteria.

(Double-circle): No water droplets, transparent, and excellent antifogging property.

(Circle): Although there is a big water drop, it is transparent and antifogging property is favorable.

(Triangle | delta): There is water droplet, it is slightly opaque, and anti-fogging property is inferior.

X: There are droplets, it is opaque, antifogging property is remarkably inferior, and it is not practical.

How to evaluate high temperature antifogging persistence:

The resin sheet for resin molded articles obtained in the test section 1 was placed in a beaker containing hot water at 80 ° C. so that the coated surface of the resin sheet modifier became the inner surface of the beaker, and was left to stand for 24 hours in an atmosphere of 5 ° C. The degree of adhesion of water droplets to the water was evaluated by the following evaluation criteria.

(Double-circle): No water droplets, transparent, and excellent antifogging property.

(Circle): Although there is a big water drop, it is transparent and antifogging property is favorable.

(Triangle | delta): There is water droplet, it is slightly opaque, and anti-fogging property is inferior.

X: There are droplets, it is opaque, antifogging property is remarkably inferior, and it is not practical.

Evaluation method of activity:

Based on JIS-K 7125, the dynamic friction coefficient was measured and evaluated according to the following reference | standard about the resin sheet for resin moldings obtained by the test section 1.

◎: dynamic friction coefficient is less than 0.25

○: dynamic friction coefficient is 0.25 or more and less than 0.30

△: dynamic friction coefficient is 0.30 or more but less than 0.35

X: dynamic friction coefficient 0.35 or more

The code | symbol in Table 1 shows the following, respectively. In addition, the composition ratio of each partial ester compound was computed from the maintenance time and area ratio of the chart of GPC (gel permeation chromatography).

<Kind of resin sheet for resin molding>

S-1: Polyethylene terephthalate resin sheet (crystallized type, thickness 300μm, surface treated with wet tension of 46mN / m by corona treatment)

S-2: Polyethylene terephthalate resin sheet (biaxially stretched type, thickness 100μm, surface treated with wet tension 42mN / m by corona treatment)

S-3: Styrene resin sheet (biaxially stretched type, thickness 300μm, surface treated with wet tension 43mN / m by corona treatment)

S-4: Polypropylene resin sheet (non-stretched type, thickness 350μm, surface treated with wet tension 45mN / m by corona treatment)

S-5: Nylon resin sheet (non-stretched type, thickness 200μm, surface treated with wet tension 45mN / m by corona treatment)

S-6: polycarbonate resin sheet (non-stretched type, thickness 400μm, surface treated with wet tension 44mN / m by corona treatment)

S-7: polymethylmethacrylate resin sheet (non-stretched type, thickness 300μm, surface treated with wet tension 45mN / m by corona treatment)

Component A, Other Classes:

A-1: partial ester of decaglycerin and lauric acid (weight ratio of ester: monoester / diester / triester and polyester = 40/31/29)

A-2: partial ester of diglycerin and oleic acid

(Weight ratio of ester: monoester / diester / triester and polyester = 3/19/78)

A-3: partial esters of glycerin and capric acid

(Weight ratio of ester: monoester / diester triester and polyester = 93/7)

A-4: partial esters of glycerin and hexanoic acid

(Weight ratio of ester: monoester / diester triester and polyester = 70/30)

A-5: partial ester of sorbitan and lauric acid

(Weight ratio of ester: monoester / diester / triester and polyester = 40/32/28)

A-6: polyoxyethylene oleyl ether (EO 13 mol)

A-7: polyethylene glycol (molecular weight 20000)

A-8: partial esters of diglycerin and stearic acid

(Weight ratio of ester: monoester / diester / triester and polyester = 35/43/22)

a-1: partial ester of sucrose and stearic acid

(Weight ratio of ester: monoester / diester triester and polyester = 70/30)

a-2: partial ester of sucrose and lauric acid

(Weight ratio of ester: monoester / diester triester and polyester = 70/30)

a-3: partial ester of sucrose and palmitic acid

(Weight ratio of ester: monoester / diester triester and polyester = 70/30)

Class of Component B:

B-1: Sodium Oleate

B-2: sodium octanoate

B-3: lithium behenate

B-4: Myristic Potassium

b-1: sodium hexanoate

C-1 to C-5 are vinyl copolymers shown in Table 2.

The code | symbol in Table 2 shows the following, respectively.

<Structural unit 1>

M-1: a methyl group R ¹ in the formula 1, R ² is an ethylene group, R ³ is a methyl group, R ⁴ is a methyl group in the vinyl monomer

M-2: R ¹ is a methyl group in the formula (I), R ² is an ethylene group, R ³ is an ethyl group, R ⁴ is ethyl group in the vinyl monomer

M-3: a vinyl monomer is R ¹ in the formula 1 is a hydrogen atom, R ² an ethylene group, R ³ is an ethyl group, R ⁴ group

<Structural unit 2 (1), structural unit 2 (2)>

S-1: 2-hydroxyethyl methacrylate

S-2: hydroxyethyl acrylate

T-1: Methyl methacrylate

T-2: ethyl acrylate

T-3: Butylacrylate

The number average molecular weight of component C was computed from the holding time and area ratio of the chart of aqueous GPC.

As shown in Table 1, in Reference Examples 5 to 9, very good results were obtained in 1 or 2 of the three performances, but the remaining performances were only good results. In Reference Examples 10 to 16, all three performances showed only good results. In the comparative example, it showed only the favorable result in any of high temperature antifog property, high temperature antifog persistence, and activity, and was inferior in other performance. In these reference examples and comparative examples, there was no balance between the three performances.

On the other hand, Examples 1-4 showed the very favorable result also in any of three performances. In this way, it is understood that the three performances are well-balanced.

Although the evaluation example about the resin sheet for resin moldings is shown in Table 1, it is the same also in the molded object using such a resin sheet for resin moldings.

As mentioned above, the Example of this invention was shown. This invention is not limited to these Examples, It is possible to comprise more Example and a modification.

Claims (5)

Including following component A, component B, and component C, Component A / component B = 29 / 71-63 / 37 (mass ratio), (component A + component B) / component C = 40 / 60-70 / 30 (mass ratio Modifiers for resin sheets for forming into shaped bodies:
Component A: at least one selected from glycerin or a condensate of glycerin (condensation degree 2 to 10) and esters of fatty acids having 8 to 24 carbon atoms;
Component B: one or more selected from fatty acid sodium salts having 8 to 18 carbon atoms;
Component C: 90-40 mass% of structural units 2 formed from 10-60 mass% of structural units 1 formed from the vinyl monomer represented by following General formula (1), and other vinyl monomers copolymerizable with the vinyl monomer represented by General formula (1) 100 mass%),
As the structural unit 2,
10-40 mass% of structural units formed from the hydroxyalkyl (meth) acrylate which has a C1-C4 hydroxyalkyl group,
10-70 mass% of structural units formed from the alkyl (meth) acrylate which has a C1-C4 alkyl group have respectively on the conditions which become 100 mass% in total with the said structural unit 1,
The vinyl copolymer of the number average molecular weights 20000-90000.
[Formula 1]

In Chemical Formula 1,
R ¹ : a hydrogen atom or a methyl group;
R ² : alkylene group having 1 to 4 carbon atoms;
R ³ and R ⁴ : an alkyl group having 1 to 4 carbon atoms The method of claim 1,
The modifier for resin sheets for shape | molding into the molded object whose ratio of component A, component B, and component C is (component A + component B) / component C = 48 / 52-64 / 36 (mass ratio). The resin sheet for resin molded objects in which the modifier for resin sheets for shape | molding with the molded object in any one of Claims 1 or ² was apply | coated to the surface at 5-200 mg / m <^2> . The method of claim 3,
The resin sheet for resin moldings which are polystyrene type, polyester type, or polyolefin type. The molded object shape | molded using the resin sheet for resin molded objects of Claim 3 or 4.