KR102167904B1 - Composition for decoration sheet and decoration sheet prepared therefrom - Google Patents

Abstract

The present invention includes a resin, a plasticizer and a stabilizer, the stabilizer includes a first stabilizer and a second stabilizer, the first stabilizer includes at least one selected from the group consisting of zinc-based compounds and barium-based compounds, The second stabilizer relates to a composition for a decor sheet, including an aluminum-magnesium-based organic compound.

Description

A composition for a decor sheet and a decor sheet prepared therefrom {COMPOSITION FOR DECORATION SHEET AND DECORATION SHEET PREPARED THEREFROM}

The present invention relates to a composition for a decor sheet and a decor sheet prepared therefrom.

In general, a decoration sheet (hereinafter referred to as a'deco sheet') refers to a sheet for expressing various decorations such as wooden patterns and abstract patterns on furniture such as a closet and a sink. Polyvinyl chloride (PVC) resin, which is conventionally used as a material for decorating sheets, has excellent physical properties and moldability, but chemical products that may cause environmental problems should be used, and polyolefin resins, which are emerging as alternative materials for this, are not molded. It is difficult and has a problem of poor appearance quality.

As an alternative to this, Korean Patent Registration No. 1,004,614 (Patent Document 1) includes a PETG alloy resin in which an elastomer resin is melt-mixed with a polyethylene terephthalate glycol (PETG) resin, and the elastomer resin is polybutyl. A deco sheet, an elastomer resin in which polyether glycol is copolymerized with a lenterephthalate (PBT) resin, is disclosed. However, the decor sheet of Patent Literature 1 has a problem of thermal deformation and susceptibility to moisture at a temperature of 70°C or higher.

In addition, the conventional composition for a decor sheet containing a PVC resin contains a plasticizer regulated by the Ministry of Environment such as diphenyl isodecyl phosphate, and has caused environmental pollution by including a phenol-based raw material.

Therefore, research and development on the composition for decor sheets excellent in gloss, strength and heat resistance is environmentally friendly, as the emission of total volatile organic compounds (TVOC) is less than 0.1 mg/m ² hours without phenol. It is a necessary situation.

Korean Patent Registration No. 1,004,614 (published on July 28, 2008)

The present invention does not contain phenol, and the emission of total volatile organic compounds (TVOC) is less than 0.1 mg/m ² hours, and is therefore an eco-friendly composition for decorating sheets and prepared from them to provide a decor sheet having excellent gloss, strength and heat resistance. do.

The present invention includes a resin, a plasticizer and a stabilizer, the stabilizer includes a first stabilizer and a second stabilizer, the first stabilizer includes at least one selected from the group consisting of zinc-based compounds and barium-based compounds, The second stabilizer provides a composition for a decor sheet comprising an aluminum-magnesium-based organic compound.

The present invention provides a decorative sheet prepared from the composition for a decorative sheet as described above.

The composition for a decor sheet according to the present invention does not contain phenol and is eco-friendly because the emission of total volatile organic compounds (TVOC) is less than 0.1 mg/m ² hours, and the decor sheet prepared from the composition is prevented from carbonization and is glossy. , It has excellent strength and heat resistance.

Hereinafter, the present invention will be described in detail.

In the present invention, the'weight average molecular weight' of the resin can be measured by a method well known in the art, for example, it can represent a value measured by the method of GPC (gel permeation chromatograph).

Composition for decor sheet

The composition for a decor sheet according to the present invention includes a resin, a plasticizer, and a stabilizer.

Suzy

The resin serves to impart coating properties to the composition for the decoration sheet.

The resin is not particularly limited as long as it is a resin commonly used in the composition for decorating sheets. For example, the resin may be a polyvinyl chloride (PVC) resin. In another example, the resin is a homopolymerized resin of vinyl chloride; Copolymer resins of vinyl chloride and other unit monomers; Alternatively, it may be a crosslinked polyvinyl chloride (PVC) resin.

In addition, the resin may have a weight average molecular weight (Mw) of 60,000 to 150,000 g/mol, and a K-value (K-value) of 60 to 70. As another example, the resin may have a weight average molecular weight of 80,000 to 130,000 g/mol, or 90,000 to 110,000 g/mol, and a K-value of 63 to 67. When the weight average molecular weight of the resin is within the above range, appropriate physical properties can be retained during rolling and molding, and when the K value is within the above range, the composition is uniformly molded in the cooling process after rolling.

The'K-value' is a value related to the intrinsic viscosity of a polyvinyl chloride (PVC) resin, and is also referred to as Fikentscher's K-value. The K value may be measured by the method of DIN EN ISO 1628-1, and the polymerization degree of polyvinyl chloride (PVC) resin may be derived from the K value through a conversion table.

The degree of polymerization of the vinyl chloride homopolymerized resin represents the number of vinyl chloride unit monomers constituting the resin by polymerization.

Plasticizer

The plasticizer serves to improve the flexibility and elasticity of the sheet produced therefrom by imparting the processability of the composition for the decor sheet containing the same.

The plasticizer is not particularly limited as long as it is usually included in the decor sheet, but, for example, phthalates plasticizer, adipate plasticizer, phosphates plasticizer, trimellitates It may be at least one selected from the group consisting of a plasticizer, an epoxy plasticizer, a glycol plasticizer, and a fatty acid plasticizer. The phthalate-based plasticizer may be one or more selected from the group consisting of a phthalates plasticizer, a phosphates plasticizer, and an epoxy plasticizer.

As another example, the phthalate plasticizer may be di(2-propylheptyl)phthalate (DPHP).

In addition, the plasticizer may have a weight average molecular weight (Mw) of 300 to 600 g/mol and a boiling point (Tb) of 230 to 280 °C. As another example, the plasticizer may have a weight average molecular weight of 400 to 500 g/mol and a boiling point of 245 to 265 °C. When the weight average molecular weight of the plasticizer is within the above range, there is an effect of imparting flexibility and workability to the polymer resin, and when the boiling point is within the above range, the effect of imparting workability to the resin without loss of raw materials during rolling and molding is achieved. have.

In addition, the plasticizer may be included in an amount of 5 to 30 parts by weight based on 100 parts by weight of the resin. As another example, the plasticizer may be included in an amount of 10 to 25 parts by weight, or 12 to 23 parts by weight based on 100 parts by weight of the resin. When the content of the plasticizer is within the above range, there is an effect of imparting flexibility and workability to the polymer resin.

In particular, the composition is a plasticizer regulated by the Ministry of Environment, DBP (Dibutyl Phthalate), BBP (butylbenzylphthalate), DEHP (Di (2-ethylhexyl) phthalate), DINP (Di-iso-nonylphthalate), DNOP (Di-n-octylphalate), DIDP Plasticizers such as (Di-isodecylphthalate) may not be included, or may be included in an amount of 0.1% by weight or less based on the total weight.

If the regulatory plasticizer is included in an amount exceeding the above, problems such as lowering of reproductive function and deformity of reproductive organs, growth inhibition and cancer, immune function inhibition, skin/bronchial disease, and hormone secretion imbalance may occur.

stabilizator

The stabilizer plays a role of imparting flexibility to a sheet manufactured from a composition for a decor sheet including the same and improving carbonization prevention properties.

The stabilizer includes a first stabilizer and a second stabilizer.

In this case, the first stabilizer includes at least one selected from the group consisting of zinc-based compounds and barium-based compounds. For example, the first stabilizer may include a zinc-based compound and a barium-based compound. As another example, the first stabilizer may include a zinc-based compound and a barium-based compound in a weight ratio of 1:1 to 1:5 or 1:1.1 to 1:4.6. When the mixing ratio of the zinc-based compound and the barium-based compound is within the above range, there is an effect of preventing carbonization of the resin mixture and preventing the raw material from sticking to the surface of the molding facility.

In addition, the zinc-based compound is selected from the group consisting of benzoic acid-zinc salt, stearic acid-zinc salt, and 2-ethylhexanoic acid-zinc salt. It may contain one or more. For example, the zinc-based compound is a group consisting of benzoic acid-zinc salt, stearic acid-zinc salt, and octylic acid-zinc salt. It may be one or more selected from.

Further, the barium-based compound is oleic acid-barium salt (9-octadecenoic acid-barium salt), stearic acid-barium salt, lauric acid-barium salt, and ricinol Lean acid-barium salt (cis-9, 12 hydroxy octadecanoic acid-barium salt) may include at least one selected from the group consisting of. For example, the barium-based compound is oleic acid-barium salt (9-octadecenoic acid-barium salt), stearic acid-barium salt, lauric acid-barium salt, and Ricinoleic acid-barium salt (cis-9, 12 hydroxy octadecanoic acid-barium salt) may be one or more selected from the group consisting of.

Meanwhile, the second stabilizer includes an aluminum-magnesium-based organic compound. For example, the second stabilizer may be made of an aluminum-magnesium-based organic compound.

In this case, the aluminum-magnesium-based organic compounds include, for example, there may be mentioned ^[2-car Bonnet Ito] hexadecafluorovanadyl hydroxy-bis (aluminum) hexahydro magnesium ^{([2-carbonato]} hexadecahydroxybis (aluminium) hexamagnesium).

In addition, the composition may include a first stabilizer and a second stabilizer in a weight ratio of 10:1 to 30:1. As another example, the composition may include a first stabilizer and a second stabilizer in a weight ratio of 10:1 to 25:1, 10:1 to 20:1, or 11:1 to 17:1. When the composition contains the first stabilizer and the second stabilizer within the above content range, there is an effect of preventing carbonization of the resin mixture, preventing the sticking of raw materials to the surface of the molding equipment, and facilitating mixing of the composition.

Further, the stabilizer may be included in an amount of 1 to 5 parts by weight based on 100 parts by weight of the resin. As another example, the stabilizer may be included in an amount of 2 to 4 parts by weight, or 2.5 to 3.5 parts by weight based on 100 parts by weight of the resin. When the content of the stabilizer is within the above range, there is an effect of preventing carbonization of the resin mixture, preventing the sticking of raw materials to the surface of the molding equipment, and facilitating the kneading of the composition.

additive

The composition for the decor sheet may further include one or more additives selected from the group consisting of sunscreens, fillers, processing aids, lubricants, and colorants.

The composition for the decor sheet may include 0.1 to 20 parts by weight of an additive based on 100 parts by weight of the resin. As another example, the composition for the decoration sheet may include 0.2 to 18 parts by weight of an additive based on 100 parts by weight of the resin.

The UV blocker blocks ultraviolet rays reaching the sheet and serves to impart light resistance to the sheet. In addition, the sunscreen agent may be a salicylic acid-based compound, a benzophenone-based compound, a benzotriazole-based compound, and a triazine-based compound, for example, benzophenone, benzhydrol, 4-hydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone, 2-hydroxy-4-octocy　benzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,3,4- Trihydroxybenzophenone, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-5-methylphenyl)benzotriazole, and the like.

The filler serves to impart color and touch to the sheet. In addition, the filler is not particularly limited as long as it is usually included in the composition for decorating sheets, and for example, silica, magnesium carbonate, calcium carbonate, hard coal, talc, magnesium hydroxide, titanium dioxide, magnesium oxide, calcium hydroxide, hydroxide Aluminum, aluminum silicate, magnesium silicate, barium sulfate, and the like.

The composition for a decor sheet according to the present invention as described above does not contain a phenolic compound and is eco-friendly because the emission of total volatile organic compounds (TVOC) is less than 0.1 mg/m ² hours.

Deco sheet

The present invention provides a decorative sheet prepared from the composition for a decorative sheet as described above.

The decor sheet is not particularly limited as long as it is a method used to make a sheet or film-type product from the composition, and may be manufactured by, for example, a calendar process. In another example, the decor sheet is a step of mixing and primary kneading the composition for the decor sheet; Secondly kneading the first-kneaded composition using a plurality of rolling rolls; Manufacturing the secondary-kneaded composition in a sheet form using a plurality of rolling rolls; Surface-treating and stretching the sheet; And the step of winding the stretched sheet; can be produced by a method comprising.

As another example, the mixing and primary kneading may be performed using a mixer and a mixing roll at 100 to 170 °C, and the secondary kneading may be performed using two or more, or four or more rolling rolls. It can be carried out at 200 °C. In addition, the surface treatment may be performed through an embo process of imparting gloss and/or a pattern to the surface of the sheet, and the stretching may be stretched 0.9 to 1.1 times in the length direction and the width direction, respectively.

The decorative sheet has a tensile strength of 20 N/㎠ or more in the longitudinal direction based on a thickness of 0.07mm, a tensile strength of 14 N/㎠ or more in the width direction, and the total amount of volatile organic compounds (TVOC) emitted is 0.1 mg/㎡ May be less than an hour. For example, the decorative sheet has a tensile strength of 20 to 50 N/cm 2 in the longitudinal direction, and a tensile strength of 14 to 35 N/cm 2 in the width direction based on a thickness of 0.07 mm, and total volatile organic compounds (TVOC) The amount of release may be 0.01 to 0.1 mg/m 2 ·hour. When the tensile strength in the longitudinal direction of the decor sheet is within the above range, it is effective to prevent the fabric from bursting during construction and tearing when cutting in the longitudinal direction. There are effects such as prevention and ease of construction on curved surfaces. In addition, when the TVOC emission amount of the decor sheet is within the above range, there is an effect of minimizing side effects such as dizziness, paralysis, convulsions, and sensory disorders.

Further, the decor sheet may have a shrinkage ratio of 3% or less in the longitudinal direction and transverse direction calculated by Equation 1 below after being left at 80° C. for 0.5 hours, and a 60° gloss of 0.5 to 30. For example, the decorative sheet may be left at 80° C. for 0.5 hours, and then the longitudinal and transverse shrinkages calculated by Equation 1 below may be -5 to 3%, respectively, and 60° gloss may be 0.5 to 25.

When the shrinkage rate by heat treatment of the decor sheet is within the above range, there is an effect of preventing shrinkage and deformation after construction, and when the 60° gloss is within the above range, there is an effect of emphasizing the embossing effect to give aesthetics.

The deco sheet according to the present invention as described above is prevented from carbonization and has excellent gloss, strength, and heat resistance.

Hereinafter, the present invention will be described in more detail through examples. However, these examples are only intended to aid understanding of the present invention, and the scope of the present invention is not limited to these examples in any sense.

[Example]

Examples 1 to 13 and Comparative Examples 1 and 2. Preparation of the composition for decoration sheet

Each component was stirred and mixed in a composition as shown in Table 1 below to prepare a composition for a decor sheet.

(Part by weight) PVC resin Plasticizer First stabilizer Second stabilizer Sunscreen Sum Example 1 81.2 15.8 2.5 0.2 0.3 100 Example 2 78.8 18.85 1.9 0.15 0.3 100 Example 3 81.2 16.55 1.8 0.15 0.3 100 Example 4 79.6 16.2 3.5 0.3 0.4 100 Example 5 83 13.2 3.3 0.2 0.3 100 Example 6 79.6 16.7 3.1 0.3 0.3 100 Example 7 83 13.7 2.9 0.1 0.3 100 Example 8 79 19.8 0.75 0.05 0.4 100 Example 9 80.3 15.4 3.7 0.3 0.3 100 Example 10 86 10.7 2.7 0.3 0.3 100 Example 11 79.6 16.7 3.3 0.1 0.3 100 Example 12 76.4 18.9 4.1 0.3 0.3 100 Example 13 83.4 15.55 0.6 0.05 0.4 100 Comparative Example 1 82.2 15 2.5 0 0.3 100 Comparative Example 2 83.7 15.8 0 0.2 0.3 100

Hereinafter, the manufacturers and product names of each component used in Comparative Examples and Examples are shown in Table 2 below.

Manufacturer and product name Remark PVC resin Manufacturer: Hanwha Chemical, Product Name: P-1000 Polyvinyl chloride
(Mw: 105,000 g/mol, non-volatile content 99% by weight) Plasticizer Manufacturer: Aekyung Petrochemical, Product Name: NEO-P Di(2-propylheptine)phthalate
(Flash point: 236℃, boiling point: 251~254℃,
Solubility 100ppm, MW 446g/mol) UV-rays
Blocker Manufacturer: Solvay, Product Name: UV-531 Benzophenone compound (Mw 326g/mol) First stabilizer Manufacturer: KD Chem, Product Name: LOX-203 Contains benzoic acid-zinc salt and oleic acid-barium salt in a weight ratio of 1: 2.9 (flash point: 220°C, specific gravity: 1.03±0.03, viscosity 200 mPa.s or less) Second stabilizer Manufacturer: KD Chem, Product Name: MW-201 [Carbonato ^2- ] Hexadecahydroxybis (aluminum) hexamagnesium
(Purity 99%, non-volatile content 99% by weight)

Test Example: Evaluation of sheet properties

4 Using this calendar, a decor sheet having a thickness of 0.077mm to 0.079mm was prepared using the compositions of Examples 1 to 13 and Comparative Examples 1 and 2. The physical properties of the prepared decor sheet were measured in the following manner, and the results are shown in Table 3.

(1) 60° gloss

The 60° gloss was measured on the decor sheet with a gloss meter.

(2) tensile strength

For the decor sheet, 6 specimens were collected using a No. 2 jig of KS M 3507 and then the tensile strength was measured using UTM.

(3) shrinkage rate

The shrinkage rate was measured by measuring the length after taking three specimens of 300mm × 300mm width × height 300mm × 300mm for the deco sheet and leaving them at 80℃±2℃ for 30 minutes.

(4) Content of regulated phthalates

Contents of regulated phthalates DBP, BBP, DEHP, DINP, DNOP and DIDP using gas chromatography-mass spectrometry (GC-MS) according to the method for quantifying phthalate plasticizers (KS M 1991) in polymer materials for decor sheets. Was measured.

(5) TVOC emissions

The total amount of volatile organic compounds released (mg/m2) over 1 hour was measured by applying a small chamber method to the decor sheet.

Average
thickness
(mm) 60°
Polish Tensile strength (N/mm ² ) Shrinkage (%) Content of regulated phthalates
(weight%) TVOC emission
(Mg/㎡) Width direction Longitudinal direction Width direction Longitudinal direction Example 1 0.077 22.3 28.2 43.6 1.02 -2.76 0 0.05 Example 2 0.078 23.1 29.3 43.6 1.08 -2.55 0 0.05 Example 3 0.077 19.8 27.2 43.6 1.15 -3.15 0 0.05 Example 4 0.077 24 26.3 43.6 1.05 -2.72 0 0.05 Example 5 0.078 26 25.8 43.6 1.09 -2.66 0 0.06 Example 6 0.077 22.28 26.5 42.6 1.52 -3.45 0 0.06 Example 7 0.078 22.28 25.9 41.6 1.63 -3.38 0 0.05 Example 8 0.077 22.28 26.2 43.6 1.03 -2.86 0 0.01 Example 9 0.077 22.28 26.7 43.6 1.04 -2.96 0 0.08 Example 10 0.079 28 15.8 29.8 2.7 -4.76 0 0.08 Example 11 0.077 29.5 19.2 28.6 2.9 -4.26 0 0.05 Example 12 0.077 26 18.8 27.8 2.9 -4.16 0 0.08 Example 13 0.077 24 19.7 24.5 2.82 -4.22 0 0.09 Comparative Example 1 0.078 36 12.5 17.2 5.6 -7.76 0 0.06 Comparative Example 2 0.077 39 12 16.8 6.2 -8.12 0 0.05

As shown in Table 3, sheets prepared from the compositions for decor sheets of Examples 1 to 13 had appropriate gloss, tensile strength and shrinkage, did not contain regulatory phthalates, and had low TVOC content. On the other hand, sheets prepared from the compositions for decor sheets of Comparative Examples 1 and 2 lacked physical properties such as gloss, tensile strength and shrinkage.

Claims (6)

Containing resins, plasticizers and stabilizers,
The stabilizer comprises a first stabilizer and a second stabilizer in a weight ratio of 10:1 to 30:1,
The first stabilizer includes at least one selected from the group consisting of zinc-based compounds and barium-based compounds,
The second stabilizer includes an aluminum-magnesium-based organic compound,
The content of the plasticizer is 5 to 30 parts by weight based on 100 parts by weight of the resin,
The total content of the first stabilizer and the second stabilizer is 1 to 5 parts by weight based on 100 parts by weight of the resin, a composition for a decor sheet. delete The method according to claim 1,
The first stabilizer comprises a zinc-based compound and a barium-based compound, a composition for decor sheet. The method of claim 3,
The first stabilizer comprises a zinc-based compound and a barium-based compound in a weight ratio of 1:1 to 1:5, a composition for a decor sheet. delete Deco sheet prepared from the composition for a decor sheet of any one of claims 1, 3 and 4.