KR102403367B1 - Low-gloss composite poly(methyl)methacrylate (PMMA)-based resin composition with improved surface texture - Google Patents

Abstract

The present invention can provide a composite poly(methyl) methacrylate-based resin composition and a molded article prepared therefrom, the molded article having a matt surface, providing a soft texture at the same time, realizing low gloss, and excellent impact resistance have an effect

Description

Low-gloss composite poly(methyl)methacrylate (PMMA)-based resin composition with improved surface texture}

The present invention relates to a composite poly(methyl) methacrylate-based resin composition and a molded article prepared therefrom, and more particularly, to a low-gloss composite poly(methyl) methacrylate with a smooth surface and a matt texture. It relates to a resin composition and a molded article prepared therefrom.

Polymethyl methacrylate (PMMA) is a plastic material used in various fields such as automobiles, home appliances, electrical and electronic devices, optical lenses, transparent films, and artificial marble because of its excellent transparency, weather resistance, scratch resistance, and colorability.

Polymethyl methacrylate (PMMA) has been widely used as an automobile exterior material due to the above advantages and particularly excellent gloss, but due to its relatively weak impact resistance and chemical resistance and high price, polymethyl methacrylate (PMMA) is ABS (Acrylonitrile) Butadiene Styrene) or ASA (Acrylic Styrene Acrylonitrile) is being replaced.

However, polymethmethyl acrylate has superior transparency and colorability than ABS or ASA, and is still widely used as a material for interiors or exteriors.

In addition, recently, as a material for interior or exterior, the demand for low-gloss polymethmethyl acrylate, which gives a soft and luxurious appearance, is increasing.

Therefore, it is necessary to develop low-gloss polymethmethylacrylate, and it is necessary to develop polymethmethylacrylate that simultaneously realizes matt properties that prevent fingerprints and dust from contacting, and furthermore, a soft texture.

Korean Patent Registration No. 10-0725940 Korean Patent No. 10-0962368

In order to solve the problems of the prior art as described above, the present invention provides a composite polymethmethylacrylate-based resin composition comprising a poly(meth)methylacrylate-based resin, an acrylic impact modifier, an acrylic bead, and a slip agent. The purpose.

Another object of the present invention is to provide a molded article having excellent impact strength produced therefrom by providing a composite polymethmethylacrylate-based resin composition comprising an acrylic impact modifier.

Another object of the present invention is to provide a low-gloss molded article prepared therefrom by providing a composite polymethmethylacrylate-based resin composition comprising acrylic beads.

Another object of the present invention is to provide a molded article having a smooth texture on the surface prepared therefrom by providing a composite polymethmethylacrylate-based resin composition including a slip agent.

The present invention includes a poly (methyl) methacrylate-based resin composition, acrylic beads, and a slip agent represented by the following formula (1),

The poly(methyl)methacrylate-based resin composition provides a composite poly(methyl)methacrylate-based resin composition comprising a poly(methyl)methacrylate-based resin and an acrylic impact modifier.

[Formula 1]

(In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ may each independently be an alkylene group having 1 to 6 carbon atoms, and m and n are 1 or more real numbers.)

In the poly(methyl)methacrylate-based resin composition according to an aspect of the present invention, the poly(methyl)methacrylate-based resin and the acrylic impact modifier may be included in a weight ratio of 5:5 to 8:2.

According to an aspect of the present invention, the acrylic beads may include 10 to 30 parts by weight based on 100 parts by weight of the poly(methyl)methacrylate-based resin composition.

According to an aspect of the present invention, the acrylic beads are acrylic crosslinked particles, and may have an average particle diameter of 2 to 60 μm.

According to one aspect of the present invention, the acrylic impact modifier has an acrylic core-shell structure, and may have an average particle diameter of 0.1 to 1 μm.

According to an aspect of the present invention, the slip agent may include 1 to 5 parts by weight based on 100 parts by weight of the poly(methyl)methacrylate-based resin composition.

According to an aspect of the present invention, the poly(methyl)methacrylate-based resin may be a homopolymer or a copolymer of a methylmethacrylate monomer.

Specifically, the copolymer may be a copolymer of one or more monomers selected from ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate and a methyl methacrylate monomer. .

According to an aspect of the present invention, the composite poly (methyl) methacrylate-based resin composition is a lubricant, a stabilizer, an antioxidant, a UV stabilizer, an optical brightener, a flame retardant, a colorant, a dye, a plasticizer, a pigment and an inorganic additive from the group consisting of It may further include one or two or more selected.

The present invention may provide a molded article prepared from the composite poly(methyl)methacrylate-based resin composition of various aspects of the present invention.

According to an aspect of the present invention, the molded article may be used as an interior or exterior material.

The composite poly(methyl) methacrylate-based resin composition of the present invention contains an acrylic impact modifier, an acrylic bead, and a slip agent, so that the texture of the surface is matt and soft, low gloss and excellent impact resistance. Very useful for manufacturing.

In addition, the molded article of the composite poly (methyl) methacrylate-based resin composition of the present invention has a matt and smooth surface, and is useful for interior or exterior materials due to its low gloss properties.

Hereinafter, the present invention will be described in more detail through embodiments or examples including the accompanying drawings. However, the following specific examples or examples are only a reference for describing the present invention in detail, and the present invention is not limited thereto, and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description herein is for the purpose of effectively describing particular embodiments only and is not intended to limit the invention.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

Also, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

Hereinafter, the composite poly(methyl)methacrylate-based resin composition of the present invention and a molded article prepared therefrom will be described.

The present invention includes a poly (methyl) methacrylate-based resin composition, acrylic beads, and a slip agent represented by the following formula (1),

The poly(methyl)methacrylate-based resin composition provides a composite poly(methyl)methacrylate-based resin composition comprising a poly(methyl)methacrylate-based resin and an acrylic impact modifier.

[Formula 1]

(In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ may each independently be an alkylene group having 1 to 6 carbon atoms, and m and n are 1 or more real numbers.)

As used herein, “alkylene” refers to a diradical of an alkane having 1 to 6 carbon atoms, and the alkylene may be linear or branched.

Specifically, in Formula 1, R ₁ and R ₂ may each independently be an alkylene having 1 to 3 carbon atoms, R ₃ and R ₄ may be independently of each other an alkylene having 3 to 5 carbon atoms, and m and n are mole fractions. m+n=1, and the ratio of the mole fractions of m and n may be 15 to 20: 20 to 40, and more specifically 15 to 20: 25 to 35.

The poly(methyl)methacrylate-based resin composition according to an aspect of the present invention may include a poly(methyl)methacrylate-based resin and an acrylic impact modifier in a weight ratio of 5:5 to 8:2, specifically The poly(methyl) methacrylate-based resin composition may include a weight ratio of the poly(methyl) methacrylate-based resin and the acrylic impact modifier in a range of 6:4 to 8:2, and more specifically, in a weight ratio of 6:4 to 7:3. may be included.

The molded article including the poly(methyl)methacrylate-based resin composition including the acrylic impact modifier in the above weight ratio has excellent impact strength under the influence of the acrylic impact modifier, so that damage may not occur.

According to an aspect of the present invention, the acrylic bead may contain 10 to 30 parts by weight based on 100 parts by weight of the poly(methyl)methacrylate-based resin composition, and specifically, the acrylic bead is a poly(methyl)methacrylate-based resin composition. It may contain 13 to 23 parts by weight based on 100 parts by weight of the resin composition.

A molded article made of the composite poly(methyl)methacrylate-based resin composition including the acrylic beads in the range of parts by weight can realize low gloss and have a matte surface.

According to an aspect of the present invention, the acrylic beads are acrylic crosslinked particles, and may have an average particle diameter of 2 to 60 μm, specifically 2 to 50 μm, more specifically 2 to 15 μm or less, more specifically 2 to 15 μm less than, more specifically 2 to 10 μm.

The molded article made of the composite poly(methyl)methacrylate-based resin composition including the acrylic beads having the above average mouth folds can prevent the surface from being too rough by reducing the unevenness, and thus the smooth texture of the slip agent. Matte texture and matte can be realized without interfering with the implementation.

According to an aspect of the present invention, the acrylic beads may be a cross-linked polymer in which polymethyl methacrylate is reacted with one or more cross-linking agents selected from divinylbenzene, ethylene glycol dimethacrylate and diethylene glycol dimethacrylate. have.

According to an aspect of the present invention, the acrylic impact modifier may have a core-shell structure, and may have an improved impact strength having a core-shell structure.

According to an aspect of the present invention, the acrylic impact modifier may have an average particle diameter of 0.1 to 1 μm, specifically, the average particle diameter of the acrylic impact modifier may be 0.1 to 0.5 μm, more specifically 0.23 to 0.26 μm.

Specifically, the acrylic impact modifier may be a copolymer of methyl methacrylate-butadiene, and more specifically, the copolymer is methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and styrene. It can be prepared by further including one or two or more selected

In one embodiment of the present invention, the slip agent may include 1 to 5 parts by weight based on 100 parts by weight of the poly(methyl)methacrylate-based resin composition, and specifically, the slip agent is a poly(methyl)methacrylate-based resin It may contain 1 to 4 parts by weight, more specifically, 1 to 3 parts by weight based on 100 parts by weight of the composition.

According to an aspect of the present invention, the poly(methyl)methacrylate-based resin may be a homopolymer or copolymer of a (methyl)methacrylate monomer.

Specifically, the copolymer includes one or more monomers selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate and a (methyl) methacrylate monomer. It may be a copolymer of, but is not limited to.

According to an aspect of the present invention, the composite poly(methyl)methacrylate-based resin composition is a lubricant, a stabilizer, an antioxidant, a UV stabilizer, an optical brightener, a flame retardant, a colorant, a dye, a plasticizer, a pigment, and an inorganic additive. It may further include one or two or more selected from.

The present invention provides a molded article prepared from the composite poly(methyl)methacrylate-based resin composition of an aspect of the present invention.

According to an aspect of the present invention, the molded article has a matte and soft surface texture. In addition, it has excellent impact resistance due to its low gloss, so it can be very usefully used as an interior or exterior material.

Hereinafter, the present invention will be described with reference to examples. That is, the present invention can be better understood by the following examples, which are for illustrative purposes of the present invention. However, the embodiments of the present invention are not intended to limit the protection scope limited by the appended claims.

<Exam item>

1. Surface roughness measurement

In accordance with the ISO 4287 standard, it was measured using the KEYENCE VHX-7000 Digital Optical Microscope at Scale 100 magnification 500 in the surface roughness measurement mode.

2. Gloss measurement

According to ISO 2813 standard, it was measured using the standard gloss of 60° among the contact light (25°, 60°, 85°) using an IAPE Glossmeter.

Examples 1-2 and Comparative Examples 1-4: Films prepared from PMMA resin composition

Polymethyl methacrylate is obtained by mixing 70 wt% of Base PMMA resin with a weight average molecular weight of 89,000 g/mol and 30 wt% of our acrylic impact modifier (LXMMA, PR 700) having an average core-shell structure particle diameter (0.2 μm). A resin composition is prepared, and the components and contents shown in Table 1 are added thereto with respect to 100 parts by weight of the polymethyl methacrylate resin composition, and mixed with a Banbury mixer for 10 minutes to obtain a composite polymethyl methacrylate resin composition prepared. Each of the prepared composite polymethyl methacrylate resin compositions was kneaded using a twin-screw extruder (32Φ, L/D=36, SM PLATEK) at a cylinder temperature of 230° C. and then pelletized, and the pellets were Film was manufactured using a film extruder.

The prepared film was shown in Table 2 by measuring the surface roughness and gloss of the test item.

Prescription Base PMMA resin
(wt%) Acrylic impact modifier
(wt%) acrylic beads
(MH-FHD) sleep agent
(Evonik, S-6441P) content
(parts by weight) Particle Size content
(parts by weight) Example 1 70 30 30 5㎛ 3 Example 2 70 30 30 15㎛ 3 Example 3 70 30 30 10㎛ 3 Example 4 70 30 30 2㎛ 3 Comparative Example 1 70 30 30 5㎛ X Comparative Example 2 70 30 30 15㎛ X Comparative Example 3 70 30 15 40㎛ X Comparative Example 4 70 30 15 60㎛ X

X means not added.

analysis Gloss (60°)
(GU) asperity texture Color average roughness
(Sa) Roughness Kurtosis (Sku) Roughness Valley Depth (Sv) Example 1 4.0 3.03 μm 2.14 μm 3.43 μm ◎ White Example 2 4.4 4.52 μm 2.42 μm 3.09 μm ○ White Example 3 4.6 3.76 μm 2.20 μm 8.47 μm ○ White Example 4 5.1 3.46 μm 2.16 μm 6.79 μm ○ White Comparative Example 1 4.4 7.06 μm 3.82 μm 4.77 μm X White Comparative Example 2 3.7 7.69 μm 4.04 μm 6.28 μm X White Comparative Example 3 6.45 7.79 μm 4.28 μm 10.39 μm X White Comparative Example 4 7.9 8.17 μm 4.8 μm 14.35 μm X White

Gloss (60°) of Table 2 is a value indicating the degree of gloss of the measurement film, and the smaller the value, the lower the gloss.

The roughness of the surface measured by Surface Roughness was expressed as three measured values. The average roughness (Sa) is a value indicating the arithmetic mean deviation, the roughness kurtosis (Sku) is a kurtosis value, and the roughness kurtosis (Sku) indicates that the height distribution is sharp, and the larger the value, the greater the roughness.

The meanings of ◎, ○, and X of the texture are as follows.

◎ = The surface is matte and the texture is very good.

○ = Matte surface and excellent soft texture.

X = The surface is matte and does not achieve a smooth texture.

When checking Examples 1 to 4 and Comparative Examples 1 to 3 of Table 2, it can be confirmed that the Gloss (60°) value is 10 GU or less to realize low gloss. Therefore, it can be confirmed that low gloss is realized in Examples and Comparative Examples including acrylic beads.

When the roughness values of Examples 1 to 4 are checked in Table 2, it can be confirmed that the average roughness (Sa) value is 5 μm or less. In addition, in terms of texture, it can be confirmed that Examples 1 to 4 realize a matte surface and a soft texture at the same time.

Checking Comparative Examples 1 to 4 that do not include a slip agent in Table 2, it can be seen that low gloss and matteness of the surface can be realized, but a soft texture cannot be realized.

Therefore, the poly(methyl) methacrylate resin including the slip agent, the acrylic impact modifier, and the acrylic beads presented in the present invention can realize low gloss and matte properties of the surface. Textures can also be implemented.

As described above, the present invention has been described by specific matters and limited examples, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and in the field to which the present invention pertains Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims to be described below, but also all those with equivalent or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention.

Claims (11)

It contains a poly (methyl) methacrylate-based resin composition, acrylic beads, and a slip agent represented by the following formula (1),
The poly (methyl) methacrylate-based resin composition includes a poly (methyl) methacrylate-based resin and an acrylic impact modifier,
The acrylic beads are a composite poly(methyl)methacrylate-based resin composition comprising 10 to 30 parts by weight based on 100 parts by weight of the poly(methyl)methacrylate-based resin composition:
[Formula 1]

In Formula 1,
R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkylene group having 1 to 6 carbon atoms, and m and n are 1 or more real numbers. The method of claim 1,
The poly(methyl)methacrylate-based resin composition is a composite poly(methyl)methacrylate-based resin composition comprising a poly(methyl)methacrylate-based resin and an acrylic impact modifier in a weight ratio of 5:5 to 8:2. delete The method of claim 1,
The acrylic beads are acrylic crosslinked particles, and the average particle diameter of the composite poly(methyl) methacrylate-based resin composition is 2 to 60 μm. The method of claim 1,
The acrylic impact modifier has an acryl-based core-shell structure and an average particle diameter of 0.1 to 1 μm. A composite poly(methyl)methacrylate-based resin composition. The method of claim 1,
The slip agent is a composite poly(methyl) methacrylate-based resin composition comprising 1 to 5 parts by weight based on 100 parts by weight of the poly(methyl) methacrylate-based resin composition. The method of claim 1,
The poly(methyl)methacrylate-based resin is a composite poly(methyl)methacrylate-based resin composition that is a homopolymer and a copolymer of a methylmethacrylate monomer. 8. The method of claim 7,
The copolymer is a composite poly(methyl) copolymer of one or more monomers selected from ethyl acrylate, n-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate and a methyl methacrylate monomer. A methacrylate-based resin composition. The method of claim 1,
The composite poly (methyl) methacrylate-based resin composition is one or two or more selected from the group consisting of a lubricant, a stabilizer, an antioxidant, an ultraviolet stabilizer, an optical brightener, a flame retardant, a colorant, a dye, a plasticizer, a pigment, and an inorganic additive Composite poly (methyl) methacrylate-based resin composition further comprising. A molded article prepared from the composite poly(methyl)methacrylate-based resin composition of any one of claims 1, 2, and 4 to 9. 11. The method of claim 10,
The molded article is an interior or exterior material.