KR20210015677A - Expandable vinyl chloride resin composition - Google Patents

Abstract

The present invention relates to an eco-friendly foamable vinyl chloride-based resin composition which has excellent foaming properties such as foaming ratio, cell stability, etc., and does not generate harmful substances such as formamide. A foamable vinyl chloride-based resin composition of the present invention can be suitably used for wall paper, foam mat, flooring material, artificial leather, or automobile interior materials.

Description

Expandable vinyl chloride resin composition TECHNICAL FIELD [EXPANDABLE VINYL CHLORIDE RESIN COMPOSITION}

The present invention relates to an eco-friendly foamable vinyl chloride resin composition having excellent foaming properties.

The vinyl chloride resin is a homopolymer of vinyl chloride and a hybrid polymer containing 50% or more of vinyl chloride, and is one of the general-purpose thermoplastic plastic resins produced by suspension polymerization and emulsion polymerization. Among them, polyvinyl chloride resins produced by emulsion polymerization are plasticizers, stabilizers, fillers, blowing agents, pigments, viscosity depressants, titanium dioxide (TiO). ₂ ) Mixing and subsidiary materials are processed into a plastisol or granule form, and through coating molding, extrusion molding, injection molding, and calendar molding, flooring, wallpaper, tarpaulin, artificial leather, toys, automobile interior materials , It is used in a wide range of fields such as coatings under automobiles.

In particular, interior interior products such as wallpaper or flooring are products that are most exposed in residential and office spaces, and more than 60% of them are manufactured using vinyl chloride resin. Recently, the main issue of wallpaper and flooring is environment-friendliness, and the criteria for judging eco-friendliness are HB grades (best, excellent, good), which are rated according to the amount of volatile organic compounds (VOCs) emitted by the Air Purification Association. 3) and whether it contains phthalate plasticizers (DEHP, BBP, DBP, DINP, etc.), which are considered suspicious substances for environmental hormones in Korea.

Among vinyl chloride resin compositions for wallpaper and flooring, plasticizer is a liquid component that occupies the largest amount. Examples of such plasticizers include phthalate products such as DEHP (Di-2-EthylHexyl Phthalate), DINP (Di-IsoNonyl Phthalate), DIDP (Di- Iso-Decyl Phthalate), BBP (Butyl Benzyl Phthalate), DBP (Di-n-butyl phthalate), and in particular DINP has been widely used.

However, phthalate-based plasticizers are suspicious of environmental hormones as an endocrine disrupter that interferes or disrupts human hormone action socially, and thus regulation is underway. Accordingly, recently, non-phthalate plasticizers such as DOTP (Dioctyl terephthalate) have been used instead of phthalate plasticizers.

On the other hand, the foamable vinyl chloride resin composition used for foam mats such as playroom mats, artificial leather, etc., previously mainly used ADCA (Azodicarbonamide) as a foaming agent, but the ADCA is formamide (Formamide), a kind of volatile organic compound during thermal decomposition. ). Accordingly, OBSH(p,p'-Oxybis(benzenesulfonyl hydrazide)) is used as a foaming agent to replace ADCA, and a foamable resin composition containing OBSH as a foaming agent and DOTP as a plasticizer is used in consideration of eco-friendliness.

However, OBSH has a relatively small amount of gas emission during foaming and a low decomposition temperature, and thus has a disadvantage in that it lacks foaming characteristics such as foaming ratio and foam cell stability compared to ADCA foaming agents under the processing conditions of general vinyl chloride resins.

Therefore, there is a need to develop an eco-friendly foamable vinyl chloride resin composition while maintaining excellent foaming properties.

The present invention provides an eco-friendly expandable vinyl chloride-based resin composition that has excellent foaming properties such as foaming ratio and foam cell stability, does not contain a phthalate plasticizer, and significantly reduces the generation of volatile organic compounds. It aims to do.

In addition, an object of the present invention is to provide a molded article comprising the expandable vinyl chloride resin composition.

In order to solve the above problems, the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) It provides a foamable vinyl chloride resin composition.

The expandable vinyl chloride resin composition may include 50 to 120 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate based on 100 parts by weight of the vinyl chloride resin.

The expandable vinyl chloride-based resin composition may include 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) based on 100 parts by weight of the vinyl chloride-based resin.

The expandable vinyl chloride resin composition contains the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) from 20:1 to 7 It can be included in a weight ratio of :1.

The vinyl chloride-based resin may have a degree of polymerization of 800 or more to less than 1,700.

Preferably, the expandable vinyl chloride-based resin composition is, based on 100 parts by weight of the vinyl chloride-based resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 to 100 parts by weight, and It may contain 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).

On the other hand, the foamable vinyl chloride resin composition may further include a stabilizer and/or a filler.

The stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds, and phosphorous acid ester compounds. It can be any one or more.

The filler may be at least one selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay.

In addition, the present invention provides a molded article comprising the foamable vinyl chloride resin composition.

The molded article may be wallpaper, foam mat, flooring, artificial leather, or automobile interior material.

The expandable vinyl chloride resin composition according to the present invention is a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) By including together, it shows excellent foaming properties. In addition, since the foamable vinyl chloride-based resin composition does not contain a phthalate-based plasticizer and ADCA, it is environmentally friendly because there is little concern about the occurrence of environmental hormones and volatile organic compounds.

Accordingly, the foamable vinyl chloride resin composition of the present invention may be suitably used for wallpaper, foam mat, flooring, artificial leather, or automobile interior materials.

1 is a photograph of a cross section of each foam sheet of Examples and Comparative Examples.
2 is a graph of measuring gelling speeds of Examples and Comparative Examples.

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form of disclosure, it is to be understood as including all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Hereinafter, a foamable vinyl chloride resin composition and a molded article will be described in more detail according to a specific embodiment of the present invention.

The foamable vinyl chloride-based resin composition according to the present invention has the insufficient foaming performance of p,p'-oxybis(benzenesulfonylhydrazide) (OBSH), di(2-ethylhexyl)cyclohexane-1,4-dicar It was conceived that it can be supplemented by using a deoxylate (DEHCH) together. In addition, since the foamable vinyl chloride-based resin composition uses OBSH, an eco-friendly foaming agent, and does not contain a phthalate plasticizer, it can be used as an eco-friendly material that greatly reduces the risk of generation of volatile organic compounds or release of environmental hormones.

The expandable vinyl chloride resin composition according to an embodiment of the present invention includes a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfuryl). Phonylhydrazide).

Throughout the present specification, the vinyl chloride-based resin refers to a vinyl chloride-based monomer alone or a (co)polymer in which a vinyl chloride-based monomer and a comonomer copolymerizable therewith are copolymerized. In addition, it may be prepared by a polymerization method such as suspension polymerization, micro-suspension polymerization, emulsion polymerization, or mini-emulsion polymerization by mixing a suspension agent, a buffer, and a polymerization initiator.

The vinyl chloride-based resin is polyvinyl chloride (PVC), and a degree of polymerization of 800 or more to less than 1,700 may be used in consideration of compatibility with an OBSH foaming agent. Alternatively, the degree of polymerization of the vinyl chloride-based resin may be 900 to 1,500. If the degree of polymerization of the vinyl chloride-based resin is too high, above 1,700, foam sheets are not formed at the temperature at which the OBSH foaming agent is foamed, and all of the vaporized foaming agent escapes and foaming may not occur smoothly. Conversely, if the degree of polymerization is less than 800, There may be a problem that the foaming does not occur because the molding is completed before the foaming agent is vaporized.

The degree of polymerization of the vinyl chloride resin can be measured according to JIS K 6720-2.

The di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate (Di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate; DEHCH) is a compound represented by the following Chemical Formula 1, and is chlorinated in the present invention. It is used as a plasticizer for vinyl resins. DEHCH has low viscosity at room temperature and low temperature, so it can realize excellent coating properties, has a fast gelling speed, and has excellent foaming properties. In addition, it is possible to minimize the generation of volatile organic compounds compared to existing phthalate plasticizers, and unlike DOTP, since it does not contain a benzene ring in the molecular structure, it is possible to reduce the potential risk.

[Formula 1]

The DEHCH may be included in an amount of 50 to 120 parts by weight, or 70 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of DEHCH is less than 50 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, the viscosity is too high and processing is difficult, and the effect of supplementing the foaming performance of OBSH cannot be obtained. In addition, if the DEHCH content exceeds 120 parts by weight based on 100 parts by weight of the vinyl chloride resin, the viscosity is too low to process, and the gelling is too slow, so that the gas generated when the foaming agent evaporates does not form a cell and escapes. There is a problem that the foamability is inferior, which is not preferable.

Preferably, the expandable vinyl chloride resin composition of the present invention contains only DEHCH as a plasticizer, and may not further contain a plasticizer other than DEHCH.

The p,p'-oxybis (benzenesulfonyl hydrazide) (p,p'-Oxybis (benzenesulfonyl hydrazide); OBSH) is a compound represented by the following formula (2), and is used as a blowing agent in the present invention.

[Formula 2]

The OBSH is preferably included in an amount of 0.5 to 12 parts by weight, or 5 to 10 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of OBSH is less than 0.5 parts by weight based on 100 parts by weight of the vinyl chloride-based resin, there is a problem that sufficient foaming does not occur, and if it exceeds 12 parts by weight, there may be a problem that the stability of the foaming cell is poor.

Unlike ADCA, OBSH is eco-friendly because it does not generate harmful components such as formamide and ammonia. However, the amount of gas released from OBSH is about 125 ml/g, which does not reach ADCA (about 220 ml/g), and the decomposition temperature is low at 157 to 160° C., and foaming performance is lower than that of ADCA under the same processing conditions. Accordingly, in the present invention, the insufficient foaming performance of OBSH is supplemented by using the above-described DEHCH as a plasticizer.

In order to secure the effect, the weight ratio of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) is 20:1 to 7 It is preferably in the range of :1, or 10:1 to 7:1. Within a range that satisfies the above weight ratio, a sufficient plasticizing effect and excellent foaming performance can be expected.

On the other hand, the foamable vinyl chloride resin composition of the present invention may use only the above OBSH as a foaming agent, and may not further contain a foaming agent other than OBSH. As described above, when only OBSH is used as a foaming agent together with a DEHCH plasticizer in the foamable vinyl chloride resin composition, more excellent foaming performance may be exhibited.

On the other hand, the expandable vinyl chloride resin composition according to an embodiment of the present invention, based on 100 parts by weight of the vinyl chloride resin, the di (2-ethylhexyl) cyclohexane-1,4-dicarboxylate 50 to 120 parts by weight, and 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) may be included.

In addition, the expandable vinyl chloride resin composition according to another embodiment of the present invention, based on 100 parts by weight of the vinyl chloride resin, the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate 70 To 100 parts by weight, and 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide).

The vinyl chloride-based resin composition may further include additives such as stabilizers and fillers. The additive may be appropriately selected according to physical properties to be improved in the vinyl chloride resin composition.

The stabilizer is added for the purpose of preventing various changes in physical properties caused by cutting and crosslinking of the main chain by separating HCl from the vinyl chloride-based resin to form a polyene structure, which is a chromophore, and Ca-Zn-based compound, K -Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds and phosphorous acid ester compounds include any one or more selected from the group consisting of.

More specific examples as a stabilizer that can be used in the present invention are Ca-Zn-based compounds; K-Zn-based compounds; Ba-Zn-based compounds; Organic Tin-based compounds such as mercaptide-based compounds, maleic acid-based compounds, or carboxylic acid-based compounds; Metallic soap-based compounds such as Mg-stearate, Ca-stearate, Pb-stearate, Cd-stearate, or Ba-stearate; Phenolic compounds; Phosphoric acid ester compounds; Or a phosphorous acid ester compound, and the like, and is optionally included depending on the purpose of use. In the present invention, it is particularly preferable to use a K-Zn-based compound, preferably a K-Zn-based complex organic compound.

The stabilizer is preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the content of the stabilizer is less than 0.5 parts by weight, there is a problem that the thermal stability is poor, and if it exceeds 5 parts by weight, there is a problem that the workability is poor.

The filler of the present invention is used for the purpose of improving the productivity and dry touch of a vinyl chloride resin composition, and is a group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay. It includes any one or more selected from.

In the vinyl chloride resin composition according to the present invention, the filler may preferably be 10 to 100 parts by weight, more preferably 20 to 50 parts by weight. When the filler is included in an amount of less than 10 parts by weight, there is a problem that dimensional stability and economy are lowered, and when it is included in an amount exceeding 100 parts by weight, the foaming surface is not good, and there is a problem that the workability is deteriorated.

The expandable vinyl chloride-based resin composition according to the present invention may be prepared by a method generally known in the art using a vinyl chloride-based resin, DEHCH as a plasticizer, OBSH as a foaming agent, and optionally additives. It is not limited.

The foamable vinyl chloride-based resin composition of the present invention includes DEHCH and OBSH together and exhibits excellent foaming properties similar to those of the existing ADCA foaming agent. Thus, the foamable vinyl chloride-based resin composition may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior materials, and the like. In particular, the expandable vinyl chloride-based resin composition of the present invention does not contain a phthalate plasticizer, and a foaming agent that generates volatile organic compounds such as formamide is greatly reduced, thereby reducing harmful substances such as playroom mats. It can be used suitably for the required field.

Meanwhile, according to another aspect of the present invention, a molded article including the vinyl chloride-based resin composition is provided. The molded article may be manufactured by additionally adding additives such as a stabilizer, a filler, and/or a foaming agent to the vinyl chloride-based resin composition according to its use. The molded article may be used as wallpaper, foam mat, flooring, artificial leather, automobile interior material, and the like.

Hereinafter, the present invention will be described in more detail by the following examples. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

[Example]

<Production of foamable vinyl chloride resin composition and foam sheet>

Example 1

With respect to 100 parts by weight of polyvinyl chloride (polymerization degree 1000), 90 parts by weight of DEHCH as a plasticizer and 10 parts by weight of OBSH as a foaming agent were weighed and mixed for 15 minutes with a mixer to prepare a foamable vinyl chloride-based resin composition (plastisol).

Example 2

A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 80 parts by weight of DEHCH was used as a plasticizer.

Example 3

A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that 70 parts by weight of DEHCH was used as a plasticizer.

Comparative Example 1

With respect to 100 parts by weight of high polymerization polyvinyl chloride (polymerization degree 1700), 90 parts by weight of dioctyl terephthalate (DOTP) as a plasticizer, 5 parts by weight of azodicarbonamide (ADCA) as a foaming agent are weighed and mixed for 15 minutes with a mixer for foamability. A vinyl chloride resin composition (plastisol) was prepared.

Comparative Example 2

With respect to 100 parts by weight of high polymerization polyvinyl chloride (polymerization degree 1700), 90 parts by weight of DOTP as a plasticizer and 10 parts by weight of OBSH as a blowing agent are weighed and mixed for 15 minutes with a mixer to prepare a foamable vinyl chloride resin composition (plastisol). I did.

Comparative Example 3

A foamable vinyl chloride resin composition was prepared in the same manner as in Example 1, except that DOTP was used as a plasticizer.

<Experimental Example>

(1) Foam sheet manufacturing and foaming property measurement

Each plastisol of Examples and Comparative Examples was coated to a thickness of 1.0 mm on paper using an applicator, and then heated in an oven at 190° C. to 230° C. for 80 to 160 seconds to form a foam sheet.

The thickness of the foam sheet was measured, and the uniformity of the foam cell was visually confirmed. 1 is a photograph of a cross section of each foam sheet.

(2) gelling speed

Each plastisol of Examples and Comparative Examples was measured for gelling speed at 120° C. using SVNC equipment. In the SVNC equipment, as the gelling proceeds, the amplitude decreases, and the gelling speed was compared and measured using the rate at which this value decreases. 2 is a graph of measuring gelling speed.

(3) Whether formamide is released

Foam sheets prepared using the plastisols of Examples and Comparative Examples were sampled in a circle shape with a radius of 3 cm, and pretreated at 40° C. for 1 hour. The gas sample generated after that was collected and the amount of formamide released was measured using Gas Chromatography.

The experimental results are summarized in Table 1 below.

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Foam sheet thickness (mm) 7.0 6.5 6.5 6.0 1.0 (not foamed) 5.0 Foam cell uniformity ◎ ◎ ◎ ○ - ◎ Gelling speed ◎ ◎ ◎ △ △ ○ Formamide emission (μg / m ³ ) - - - 4031.85 - -

(Very High) ◎> ○> △> X (Very Low)

The most important thing in foam products is foamability. Foaming refers to the surface condition of the product, the foaming ratio, the size of the foaming cell and the uniformity of the foaming cell.

As a result of the experiment, the foamable vinyl chloride resin composition of Examples 1 to 3 was environmentally friendly, and exhibited equal or higher foaming characteristics while having excellent gelling speed compared to the conventional vinyl chloride resin composition containing the ADCA foaming agent and the DOTP plasticizer. I could confirm. However, when the combination of the DEHCH plasticizer and the OBSH foaming agent is not satisfied as in Comparative Examples 2 and 3, it can be seen that foaming does not occur, foaming property is poor, and the gelling speed is lowered.

Claims (11)

A foamable vinyl chloride resin composition comprising a vinyl chloride resin, di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide). The method of claim 1,
An expandable vinyl chloride resin composition comprising 50 to 120 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate based on 100 parts by weight of a vinyl chloride resin. The method of claim 1,
An expandable vinyl chloride resin composition comprising 0.5 to 12 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide) based on 100 parts by weight of the vinyl chloride resin. The method of claim 1,
Effervescent chloride containing the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and p,p'-oxybis(benzenesulfonylhydrazide) in a weight ratio of 20:1 to 7:1 Vinyl resin composition. The method of claim 1,
The vinyl chloride-based resin has a degree of polymerization of 800 or more to less than 1,700 expandable vinyl chloride-based resin composition. The method of claim 1,
Based on 100 parts by weight of the vinyl chloride resin,
70 to 100 parts by weight of the di(2-ethylhexyl)cyclohexane-1,4-dicarboxylate, and
Foamable vinyl chloride resin composition comprising 5 to 10 parts by weight of the p,p'-oxybis (benzenesulfonyl hydrazide). The method of claim 1,
A foamable vinyl chloride resin composition further comprising a stabilizer and/or a filler. The method of claim 7,
The stabilizer is selected from the group consisting of Ca-Zn-based compounds, K-Zn-based compounds, Ba-Zn-based compounds, organic Tin-based compounds, metallic soap-based compounds, phenolic compounds, phosphoric acid ester compounds, and phosphorous acid ester compounds. Any one or more foamable vinyl chloride resin composition. The method of claim 7,
The filler is any one or more selected from the group consisting of calcium carbonate, talc, titanium dioxide, kaolin, silica, alumina, magnesium hydroxide, and clay. A molded article comprising the vinyl chloride resin composition of any one of claims 1 to 9. The method of claim 10,
Molded articles that are wallpaper, foam mats, flooring, artificial leather, or automotive interiors.

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