JPH0371981B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is an ethylene-vinyl acetate copolymer (hereinafter referred to as
(abbreviated as EVA) or EVA and polyethylene as main components, and contains a low molecular weight propylene-ethylene copolymer oxide component, a tackifying resin, a flame retardant, and a processability improver selected from fatty acid amide, polyethylene glycol, and hydrogenated castor oil. This product relates to a laminate material for the interior of vehicles, etc., in which a blended composition or a composition containing a rubber component is applied to a woven or knitted fabric, and the purpose is to improve the texture of the woven or knitted fabric and the workability during interior decoration without any loss,
The object of the present invention is to obtain an interior material that prevents air permeability. In recent years, the skin of interior materials such as ceilings, seats, and door trims of automobiles and other vehicles has been designed to give a sense of luxury.
Alternatively, in order to improve livability, woven or knitted fabrics such as polyester tricot are increasingly being used. However, since woven and knitted fabrics are breathable, they act as a filter and have the problem of being very easily contaminated. As a method of preventing the breathability of woven and knitted fabrics, backing of plastic sheets has been considered and is currently being used in some cases, but this has not always been satisfactory. The performance required for a backing material is to adhere well to woven or knitted fabrics, and not to impair the texture of woven or knitted fabrics, that is, to have good strength, flexibility, elasticity, heat resistance, and workability during interior decoration. Furthermore, an essential condition is that it has flame retardancy. Specifically, what is currently being used is:
One example is the backing of polyvinyl chloride sheets, but since polyvinyl chloride does not adhere well to woven or knitted fabrics, adhesives must be used. Furthermore, it has the disadvantage of impairing the feel of woven and knitted fabrics due to problems such as elasticity. Furthermore, in recent years, there has been a call for the weight of automobiles to be reduced in order to improve fuel efficiency, but polyvinyl chloride has a high specific gravity as a plastic material, and this poses a problem in terms of reducing the weight of automobiles. Also, backing of an acrylic resin emulsion has been considered, but since it is an emulsion, it has the problem that it must be backed with a considerable thickness in order to prevent air permeability. The present inventors have conducted repeated research to develop a material that satisfies all of the above performance as a bucking material.
By first using as a backing material a composition containing EVA or EVA and polyethylene as the main components and containing a tackifying resin, a flame retardant, and a processability improver selected from fatty acid amide, polyethylene glycol, and hydrogenated castor oil. We have filed a patent application for an interior material that prevents air permeability without impairing the texture of woven or knitted fabrics or the workability of interior decoration. (JP 58-162344) Although the present invention has superior characteristics compared to polyvinyl chloride and acrylic emulsion, it cannot necessarily be said that it has sufficient performance. Therefore, the present inventors conducted further intensive research, and as a result, they arrived at the present invention. That is, the present invention consists of (1) EVA or EVA containing up to 30% by weight of polyethylene, a resin component whose total vinyl acetate content is 50 to 94% by weight, and an acid value of 50 to 94% by weight; 1 to 20, low molecular weight propylene with an average molecular weight of 500 to 10,000 and an ethylene component of 1 to 20% by weight.
3 to 20% by weight of an ethylene copolymer oxide, 3 to 30% by weight of a tackifying resin with a ring and ball softening point of 95 to 140°C, or (2) 30 to 91% by weight of the resin component, the propylene-
Consists of 3-20% by weight of ethylene copolymer oxide, 3-20% by weight of the rubber component, and 3-30% by weight of the adhesive resin, and has a melting point of 90°C based on the total amount of (1) or (2). 3 to 50% by weight of a flame retardant with a ring and ball softening point of 95°C or higher, fatty acid amide, polyethylene glycol,
Processability improver selected from hydrogenated castor oil from 0.05 to
Contains 2% by weight and has a melt flow rate of 2 to 150g/
20-150μ of the composition in 10 minutes
This is a laminated material for the interior of vehicles, etc., made by backing a woven or knitted fabric in the range of m. To describe the present invention more specifically, the physical properties of EVA or a mixture of EVA and polyethylene, which is the main component of the backing material of the present invention, vary greatly depending on the vinyl acetate content contained therein, and exhibit the characteristics of the present invention. In order to achieve this, products with a specific vinyl acetate content must be used.
-30% by weight, preferably 7-25% by weight. If the vinyl acetate content is less than 5% by weight, adhesion to woven or knitted fabrics will be poor, flexibility,
It is not preferable because it reduces elasticity and workability during interior decoration. In addition, if the vinyl acetate content is 30% by weight or more, it will have good adhesion to woven or knitted fabrics, flexibility, stretchability, and workability during interior decoration, but it will not be heat resistant and will soak into woven or knitted fabrics at high temperatures. This is undesirable because it causes the air to become airy.
Also, the ratio of EVA and polyethylene is EVA100~
70% by weight, polyethylene 0-30% by weight. If the polyethylene content is 30% by weight or more, flexibility, elasticity, and workability during interior decoration will decrease, which is undesirable. Polyethylene here refers to low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, etc.
Preferably it is low density polyethylene. The low molecular weight propylene-ethylene copolymer oxide is an essential component for the purpose of adding adhesiveness and heat resistance. Specifically, a low molecular weight propylene-ethylene copolymer oxide has an average molecular weight of 500 to 10,000, an acid value of 1 to 20, and an ethylene component of 1 to 20% by weight. If the average molecular weight is less than 500, the heat resistance effect will not be exhibited, which is not preferable. Moreover, if it is 10,000 or more, flexibility, stretchability, and workability during interior decoration are reduced, which is undesirable. If the acid value is less than 1, adhesion to woven or knitted fabrics will deteriorate, which is undesirable. Further, if it is 20 or more, no improvement in adhesion to woven or knitted fabrics is observed, so there is no need for it to be 20 or more. If the ethylene component is less than 1% by weight, flexibility, stretchability, and workability during interior decoration will deteriorate, which is not preferable. Further, if it exceeds 20% by weight, heat resistance decreases, which is not preferable. Further, the low molecular weight propylene-ethylene copolymer oxide is limited to those having isotactic regularity from the viewpoint of heat resistance. The proportion of the low molecular weight propylene-ethylene copolymer oxide is 3 to 20% by weight based on the total amount of the resin component, the tackifying resin, and the low molecular weight propylene-ethylene copolymer, or the total amount of this and the rubber component. %
Preferably it is 4 to 15% by weight. If the proportion of the low molecular weight propylene-ethylene copolymer oxide is 3% by weight or less, it is insufficient to exhibit the effects of adhesion and heat resistance. Moreover, if it is 20% by weight or more, there will be no problem with adhesion or heat resistance, but flexibility will decrease, which is not preferable. The rubber component is added for the purpose of further adding flexibility and heat resistance, and the effect of the present invention becomes more pronounced by adding the rubber component. Specifically describing the rubber components, natural rubber, a homopolymer obtained by polymerizing diene monomers,
Copolymers of diene monomers and copolymerizable monomers, olefin elastomers, etc., such as butadiene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene copolymers, styrene-butadiene-styrene block copolymers, Styrene-isoprene copolymer, styrene-
Examples include isoprene-styrene block copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene rubber, etc., and one type or a mixture of two or more of these can be used. In addition, the ratio of the rubber component is the resin component, the low molecular weight propylene
The amount is 3 to 30% by weight based on the total amount of the ethylene copolymer oxide, the tackifying resin, and the rubber component. If the proportion of the rubber component is 3% or less, it is insufficient to exhibit the effects of flexibility and heat resistance. Moreover, if it is more than 20% by weight, it is not preferable because not only the adhesion to the woven or knitted fabric decreases, but also the processability during buckling decreases. Tackifying resin is an essential component for adding adhesion and flexibility to woven or knitted fabrics. Specifically, tackifying resins include polymerized rosin, hydrogenated rosin, modified rosin or rosin derivatives such as rosin ester, terpene resin, terpene modified product,
Examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, alicyclic hydrocarbon resins, etc., and these resins can be used singly or as a mixture of two or more, but in this case, resins with a ring and ball softening point of 95 to 140°C It is mandatory to use In other words, if the ring and ball softening point is 95° C. or lower, it is undesirable because it will not have heat resistance and will soak into woven or knitted fabrics at high temperatures, thereby making them breathable. Also, the ring and ball softening point is
If the temperature is 140° C. or higher, the compatibility with the resin component decreases, resulting in a decrease in strength, flexibility, elasticity, and workability during interior decoration, which is not preferable. The ratio of the tackifying resin to the resin component, the low molecular weight propylene
The amount is 3 to 30% by weight, preferably 5 to 20% by weight, based on the total amount of the ethylene copolymer oxide or the rubber component. If the proportion of the tackifying resin is less than 3%, it is not preferable because the adhesion to woven or knitted fabrics decreases. Moreover, if it is 30% by weight or more, not only is no improvement in adhesion to woven or knitted fabrics observed, but rather problems such as a decrease in compatibility with the resin component and a decrease in processability during backing processing are preferable. do not have. Interior materials for vehicles such as automobiles must pass flame retardant standards (MVSS.No. 302) from the standpoint of respecting human life, and the laminated material of the present invention must also pass flame retardant standards. For this purpose, it is necessary to make the woven or knitted fabric flame retardant, but unless the backing material is made flame retardant, it will be difficult for the laminated material to pass the flame retardant standards.
Therefore, a flame retardant is an essential component in the present invention.
Here, it is necessary to select a flame retardant that has heat resistance, and must have a melting point of 90℃ or higher or a ring and ball softening point.
Must be above 95℃. Specific examples of flame retardants include chlorinated paraffin, chlorinated polyethylene, perchloropentacyclodecane, hexabromobenzene, pentabromoethylbenzene, tetrabromobisphenol A, tetrabromophthalic acid halide, and tetrabromophosphoric acid. Halide, hexabromodiphenyl ether, pentabromodiphenyl ether, decabromodiphenyl ether, tris(2,3-dibromopropyl)isocyanurate, 2,2-bis(4-hydroxyl 3,5-dibromophenyl)
Examples include propane, ethylene bistri(2-cyanoethyl)phosphonium bromide, aluminum hydroxide, etc., and these can be used alone or in a mixture of two or more. Further, when these flame retardants and antimony trioxide are used in combination, the flame retardant effect is further improved. The amount of flame retardant to be added is 3 to 3 to 100% of the total amount of the low molecular weight propylene-ethylene copolymer oxide, the tackifying resin, or the total amount of this and the rubber component.
50% by weight, preferably 4-40% by weight. If it is less than 3% by weight, the flame retardant effect will not be improved, which is not preferable. Moreover, the flame retardant effect is sufficient at 50% by weight, and there is no need to add more than that. The processability improver in the present invention serves to prevent blocking of products, improve slip properties, etc., and is an essential component of the composition of the present invention. Specific examples of processability improvers include fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, polyethylene glycol, hydrogenated castor oil, etc. One type or a mixture of two or more of these can be mentioned. Can be used.
The amount of these processability improvers added is based on the resin component, the low molecular weight propylene-ethylene copolymer oxide,
The amount is 0.05 to 2% by weight, preferably 0.1 to 1% by weight, based on the total amount of the tackifying resin, the rubber component, the rubber component, and the tackifying resin. If the amount added is less than 0.05% by weight, the effect of the addition will be small and the effect as a processability improving agent will not be exhibited, which is not preferable. If it exceeds 2% by weight, it is not preferable because the adhesion strength to woven or knitted fabrics decreases. In the present invention, the melt flow rate of the composition must also be specified. The melt flow rate of the composition is measured by the melt flow rate measurement method specified in JISK6730, and the value is 2 to 2.
150g/10 minutes, preferably in the range of 5 to 100g/10 minutes. If the melt flow rate is less than 2 g/10 minutes, it is not preferable because adhesion to woven or knitted fabrics is poor, flexibility, stretchability, and workability during interior decoration are impaired. Moreover, if it exceeds 150g/10 minutes, the heat resistance will decrease and it cannot be used. Furthermore, in the present invention, when backing the composition onto a woven or knitted fabric, the thickness of the composition must be specified. The thickness of the composition is 20-150μ
If the thickness is less than 20 μm, the air permeability prevention effect will be weakened due to pinholes in the composition sheet, which is not preferable. Moreover, if it is 150 μm or more, the flexibility and stretchability of the woven or knitted fabric and the workability during interior decoration are impaired, which is not preferable. The composition of the present invention can be easily produced by pre-mixing predetermined amounts of the components in a solid state and then melting and shear-mixing them in a heated roll, Hanbury mixer or extruder. Further, an antioxidant such as 2,6-di-t-butyl para-cresol may be added as necessary. In the present invention, a sheet of the composition is prepared in advance by an inflation method, a T-die method, a calendar method, etc. which are generally used in the industry, and this sheet is subjected to thermal lamination, It can be obtained by bonding using means such as hot press. Alternatively, it can also be obtained by directly backing the composition onto a woven or knitted fabric by extrusion lamination. According to extrusion lamination method 1
This is a simpler method as it allows for backing during the process. The interior laminate material made by packing the composition of the present invention on a woven or knitted fabric can prevent the breathability of the woven or knitted fabric without impairing the feel of the woven or knitted fabric or the workability during interior decoration.
Moreover, since backing can be performed using commonly used processing methods, an extremely effective laminated material can be provided. Another feature of the composition according to the present invention is that it can be welded. The present invention will be specifically explained below using Examples. Example 1 EVA with vinyl acetate content of 20% by weight, 75% by weight,
Low molecular weight propylene-ethylene copolymer oxide with average molecular weight 3500, acid value 3.5, ethylene content 6% (product name Viscoll RT-200) 10% by weight, alicyclic hydrocarbon resin with ring and ball softening point 125℃ (product Name Alcon P-125) 15% by weight, based on the total amount of these,
10% by weight of decabromodiphenyl ether having a melting point of 301°C and 0.2% by weight of erucic acid amide were mixed and kneaded and extruded using an extruder to form pellets. The melt flow rate of this pellet was 63 g/10 minutes.
This composition was prepared using a cylinder diameter of 115 mm, L/D = 25,
Using an extruder equipped with a straight manifold die (resin temperature 240°C, take-off speed 20 m/min), polyester tricot was backed to a thickness of 50 μm. Example 2 The composition of Example 1 was used in a cylinder with a diameter of 40 mm and L/D.
A casting film of 50 μm was obtained using an extruder of 22 mm. This film was thermocompressed using a thermal laminator (compression temperature 130℃, line speed
10m/min), the polyester tricot was punched. Example 3 70% by weight of EVA used in Example 1, 5% by weight of low molecular weight propylene-ethylene copolymer oxide, and ethylene-propylene rubber (trade name: JSREP)
-02P) Pelletization was performed in the same manner as in Example 1 except that 10% by weight was used. The melt flow rate of this pellet was 46 g/10 minutes. This composition was subjected to backing in the same manner as in Example 1. Example 4 Pelletization was carried out in the same manner as in Example 3, except that a terpene phenol copolymer (trade name: YS Polyster T130) having a ring and ball softening point of 130°C was used as the tackifying resin. The melt flow rate of this pellet was 45 g/10 minutes. This composition was subjected to backing in the same manner as in Example 1. Example 5 Pelletization was carried out in the same manner as in Example 3 except that a styrene-butadiene-styrene block copolymer was used as the rubber component. The melt flow rate of this pellet was 35 g/10 minutes. This composition was subjected to backing in the same manner as in Example 1. Comparative Example 1 Pelletization was carried out in the same manner as in Example 1 except that EVA containing 35% by weight of vinyl acetate was used. The melt flow rate of this pellet was 86 g/10 minutes. This composition was subjected to backing in the same manner as in Example 1, except that the resin temperature during processing was 160°C. Comparative Example 2 Pelletization was carried out in the same manner as in Example 1, except that the EVA used in Example 1 was 60% by weight and the low molecular weight propylene-ethylene copolymer oxide was 25% by weight. The melt flow rate of this pellet is
It was 95g/10 minutes. This composition was packaged in the same manner as in Example 1. Comparative Example 3 Pelletization was carried out in the same manner as in Example 1, except that an alicyclic hydrocarbon resin (trade name Alcon P-70) having a ring and ball softening point of 70°C was used as the tackifying resin. The melt flow rate of this pellet is
It was 64g/10 minutes. This composition was subjected to backing in the same manner as in Example 1. Comparative Example 4 Pelletization was performed in the same manner as in Example 1 except that the flame retardant used in Example 1 was used in an amount of 2% by weight. The melt flow rate of this pellet was 64 g/10 minutes. This composition was subjected to bagging in the same manner as in Example 1. Comparative Example 5 Backing was carried out in the same manner as in Example 1 except that the backing thickness was 200 μm. The evaluation of the laminate materials described in Examples and Comparative Examples is shown in the table below.

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Claims (1)

[Scope of Claims] 1 Consists of an ethylene-vinyl acetate copolymer or an ethylene-vinyl acetate copolymer containing up to 30% by weight of polyethylene, the total vinyl acetate content of which is 5% by weight.
~30wt% resin component 50~94wt%, average molecular weight
500-10000, acid value 1-20, ethylene component 1-20
3-20% by weight of low molecular weight propylene-ethylene copolymer oxide, 3-30% by weight of a tackifying resin with a ring and ball softening point of 95-140℃, a melting point of 90℃ or higher or a ring and ball softening point of 95℃ or higher. 3 to 50% by weight of the flame retardant based on the total amount of the resin component, the low molecular weight propylene-ethylene copolymer oxide, and the tackifying resin;
0.05 to 2% by weight of a processability improver selected from fatty acid amide, polyethylene glycol, and hydrogenated castor oil based on the total amount of the resin component, the propylene-ethylene copolymer oxide, and the tackifying resin; A laminate material for the interior of vehicles, etc., which is obtained by backing a woven or knitted fabric with a composition having a melt flow rate of 2 to 150 g/10 minutes to a thickness in the range of 20 to 150 μm. 2 Consisting of ethylene-vinyl acetate copolymers or ethylene-vinyl acetate copolymers containing up to 30% by weight of polyethylene, the total vinyl acetate content of which is 5%.
~30wt% resin component 30~91wt%, average molecular weight
500-10000, acid value 1-20, ethylene component 1-20
3-20% by weight of low molecular weight propylene-ethylene copolymer oxide, 3-20% by weight of rubber component, 3-30% by weight of tackifying resin with ring and ball softening point of 95-140°C, melting point of 90°C or higher. Alternatively, a flame retardant with a ring and ball softening point of 95°C or higher is added to the resin component, the low molecular weight propylene
Ethylene copolymer oxide, 3 to 50% by weight based on the total amount of the rubber component and the tackifying resin, and a processability improver selected from fatty acid amide, polyethylene glycol, and hydrogenated castor oil to the resin component and the propylene. - A composition comprising an ethylene copolymer oxide, 0.05 to 2% by weight based on the total amount of the rubber component and the tackifying resin, and having a melt flow rate of 2 to 150 g/10 minutes. A laminated material for the interior of vehicles, etc., made by backing a woven or knitted fabric with a thickness in the range of 20 to 150 μm.