JP3170370B2 - Interior materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]

The present invention relates to an interior material, and more particularly, to an interior material having excellent adhesive strength and heat resistance, particularly excellent in adhesive strength when bonded at a low temperature and heat creep resistance at a high temperature.

[0002]

2. Description of the Related Art As interior materials for automobiles, vehicles, ships, etc., and as interior materials for enhancing the livability and aesthetics of the interior of buildings such as dwellings, such materials are known. A laminate is used in which a skin material and a substrate material for retaining and enhancing the functionality are bonded. This laminate can be manufactured by bonding the skin material and the substrate material using a solvent-based adhesive.
It takes much time and labor in working processes such as drying and aging, and in recent years environmental problems have been emphasized. However, there are problems such as occupational health and fire due to organic solvents, and it is difficult to say that it is an appropriate manufacturing method. For this reason, instead of the solvent-based adhesive, ethylene-acrylic ester-maleic anhydride terpolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer or low-melting copolymer nylon is used. Although a heat-sensitive adhesive resin is used, a sufficiently satisfactory laminate has not yet been obtained. That is, the heat-sensitive adhesive resin is
In general, the adhesive strength is insufficient compared with the solvent-type adhesive and the heat-resistant creep property is often lacking.
) Is prone to sagging and peeling if left for a long time. In addition, when the skin material and the substrate material are bonded together, if the heating temperature is set to a relatively high temperature, the bonding strength can be increased, but in this case, there is a disadvantage that the skin agent is easily damaged. On the other hand, there is a heat-sensitive adhesive resin which does not have these disadvantages, but has a disadvantage that the price is expensive and its use is limited in terms of cost. As described above, it can be used as an interior material for automobiles and dwellings, and has no problems in the manufacturing process such as workability and environmental issues.
An interior material that has excellent adhesive strength, especially when bonded at low temperature, can prevent damage to the skin agent, exhibits good heat creep resistance, and is satisfactory in terms of cost, has not yet been developed. It is a fact.

[0003]

In view of the above circumstances, the present inventors have made intensive studies to develop an interior material composed of a laminate that has solved the conventional disadvantages. as a result,
A laminate bonded through an adhesive layer made of a thermoplastic resin composition containing a specific ethylene-based multi-component copolymer and a salt of an organic carboxylic acid and a specific metal as a main component has good adhesive strength and heat resistance Was found to have. The present invention has been completed based on such findings. That is, the present invention comprises a laminate in which a skin material is adhered to a substrate material via an adhesive layer, and the adhesive layer comprises (A) ethylene and a radical polymerizable acid anhydride and other radical polymerizable comonomers. Wherein the proportion of units derived from the radical polymerizable acid anhydride in the ethylene-based multi-component copolymer is 0.1 to 5% by weight and is derived from other radical polymerizable comonomers. Resin composition containing an ethylene-based multi-component copolymer having a proportion of a unit of 3 to 50% by weight and (B) a salt of an organic carboxylic acid and a metal belonging to Group IA, IIA or IIB of the periodic table The present invention provides an interior material characterized by comprising:

As described above, the thermoplastic resin composition constituting the adhesive layer of the interior material according to the present invention comprises an ethylene-based multi-component copolymer as the component (A) and an organic carboxylic acid as the component (B). And a salt of a metal belonging to Group IA, IIA or IIB of the periodic table. The ethylene-based multi-component copolymer as the component (A) in the thermoplastic resin composition is a multi-component copolymer comprising ethylene, a radical-polymerizable acid anhydride, and a radical-polymerizable comonomer other than the above-described radical-polymerizable acid anhydride. It is united. Here, the radical polymerizable acid anhydride is a compound having one or more radically polymerizable unsaturated bonds and one or more acid anhydride groups in a molecule, and capable of introducing an acid anhydride group into the molecule by polymerization. Means The acid anhydride group is preferably cyclic. Examples of such a compound include maleic anhydride, itaconic anhydride, endic acid anhydride, citraconic anhydride, dodecenyl succinic anhydride, 1-butene-3,4-dicarboxylic anhydride, and a compound having at most 18 carbon atoms. Alkenyl succinic anhydride having a double bond at the terminal and alkadienyl succinic anhydride having a double bond at the terminal having at most 18 carbon atoms. These may be used alone or in combination of two or more. Among these, maleic anhydride and itaconic anhydride are particularly preferred. The proportion of units derived from the radically polymerizable acid anhydride in the component (A) is in the range of 0.1 to 5% by weight, preferably 0.5 to 4.5% by weight.
It is in the range of 5% by weight, more preferably in the range of 1.0 to 4.0% by weight. Here, the ratio of the radical polymerizable acid anhydride is 0.
If it is less than 1% by weight, good adhesive strength cannot be obtained due to insufficient adhesiveness. On the other hand, if it exceeds 5% by weight, it becomes difficult to produce an ethylene copolymer, which is not practical.

There are various compounds as radical polymerizable comonomers other than radical polymerizable acid anhydrides, for example, ethylenically unsaturated ester compounds, ethylenically unsaturated amide compounds, ethylenically unsaturated acid compounds, and ethylenically unsaturated acid compounds. Examples include a saturated ether compound, an ethylenically unsaturated hydrocarbon compound, and other compounds. When these are specifically described, as the ethylenically unsaturated ester compound,
For example, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, methyl fumarate, ethyl fumarate, propyl fumarate, butyl fumarate Dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, methyl maleate, ethyl maleate, propyl maleate, butyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, etc. No.
Examples of the ethylenically unsaturated amide compound include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, N- Hexyl (meth) acrylamide, N-octyl (meth) acrylamide; N, N-dimethyl (meth) acrylamide; N, N-diethyl (meth) acrylamide and the like. Examples of the ethylenically unsaturated acid compound include (meth) acrylic acid, fumaric acid, and maleic acid. Examples of the ethylenically unsaturated ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octadecyl vinyl ether, and phenyl vinyl ether. Examples of the ethylenically unsaturated hydrocarbon compound include styrene, α-methylstyrene, (meth) acrylonitrile, acrolein, crotonaldehyde, trimethoxyvinylsilane, triethoxyvinylsilane, vinyl chloride, vinylidene chloride, norbornene, and butadiene. . Among these,
(Meth) acrylic esters and (meth) acrylic acid are particularly preferred compounds. These comonomers may be used alone or in combination of two or more. The proportion of the unit derived from the radical polymerizable comonomer in the component (A) is in the range of 3 to 50% by weight, preferably in the range of 4 to 45% by weight, and more preferably in the range of 5 to 40% by weight. . Here, when the proportion of the radical polymerizable comonomer is less than 3% by weight, the crystalline melting point of the ethylene-based multi-component copolymer does not become sufficiently low, and a good bonding strength at the time of low-temperature bonding, which is a feature of the present invention, is sufficiently ensured. Can not do it. If it exceeds 50% by weight, the handling of the resin becomes difficult and the heat resistance of the product is reduced.

In producing the ethylene-based multi-component copolymer as the component (A), it is basically possible to utilize ordinary high-pressure low-density polyethylene production equipment and techniques. Generally, the bulk polymerization method is used to obtain 70
At a polymerization pressure of 0 to 3,000 atm, preferably 1,000 to 2,500 atm, and at 100 to 300 ° C, preferably 15 to
It is produced by radical polymerization at a polymerization temperature of 0 to 270 ° C. When the polymerization pressure is lower than 700 atm, the molecular weight of the polymer becomes low, and the moldability and the resin properties of the resin composition deteriorate.
On the other hand, when the pressure exceeds 3,000 atm, it only increases the production cost and is practically meaningless. When the polymerization temperature is 10
If the temperature is lower than 0 ° C., the polymerization reaction will not be stable, and the conversion to the copolymer will decrease, which is economically problematic. On the other hand, when the temperature exceeds 300 ° C., the molecular weight of the copolymer decreases, and at the same time, the risk of a runaway reaction occurs. It is preferable to use a vessel type reactor as the polymerization apparatus. In particular, radical polymerizable acid anhydrides have poor polymerization stability, and therefore require a high degree of uniformity in the reactor. If necessary, a plurality of reactors can be connected in series or in parallel to carry out multistage polymerization.
Further, by dividing the inside of the reactor into a plurality of zones, more precise temperature control can be performed.

The production of the ethylene multi-component copolymer is carried out in the presence of at least one free-radical initiator under the reaction conditions described above. Here, specific examples of the free radical initiator include oxygen; dialkyl peroxides such as di-t-butyl peroxide, t-butyl cumyl peroxide, and dicumyl peroxide; acetyl peroxide, i-butadiene. Diacyl peroxides such as noyl peroxide and octanoyl peroxide; peroxy-dicarbonates such as di-i-propylperoxy-dicarbonate and di-2-ethylhexylperoxy-dicarbonate; t-butyl peroxypivalate; Peroxyesters such as t-butylperoxylaurate; ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis-t-butylperoxycyclohexane, 2,2-bis-t-butylperoxy Peroki such as octane Ketal; t-
Hydroperoxides such as butyl hydroperoxide and cumene hydroperoxide; and azo compounds such as 2,2-azo-i-butyronitrile. In the polymerization, various chain transfer agents can be used as a molecular weight regulator. As the chain transfer agent, for example,
Olefins such as propylene, butene and hexene; paraffins such as ethane, propane and butane; carbonyl compounds such as acetone, methyl ethyl ketone and methyl acetate;
Examples thereof include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

[0008] The ethylene-based multi-component copolymer produced in this manner melts at a relatively low temperature and has a low physicochemical interaction and reactivity with various base materials (including skin materials and substrate materials). Because of the richness, even when the interior material of the present invention is manufactured by low-temperature molding, it plays a large role in securing high adhesive strength.

[0009] The organic carboxylic acid as the component (B) in the above-mentioned thermoplastic resin composition is combined with the group IA, IIA or IIB of the periodic table.
A salt with a metal belonging to the group III means an organic carboxylic acid as a salt of the periodic table I.
A compound which belongs to Group A, IIA or IIB and is completely or partially neutralized with a metal. Various organic carboxylic acids can be used as the above organic carboxylic acid. For example, lauric acid, myristic acid, stearic acid, palmitic acid, decanoic acid, pentadecanoic acid, eicosanoic acid, docosanoic Acids, tricosanoic acid, triacontanoic acid, suberic acid, azelaic acid, sebacic acid, hexadecandioic acid, etc., having 10 or more (usually 10 to 40) saturated fatty acids; oleic acid, erucic acid, linolein Acids, linolenic acid, arachidonic acid and the like having 10 or more carbon atoms (usually unsaturated fatty acids having 10 to 40 carbon atoms;
High molecular carboxylic acids such as a copolymer of ethylene and (meth) acrylic acid can be given. On the other hand, metals that form salts with organic carboxylic acids are group IA, group IIA or
It is a metal belonging to Group IIB. The component (B) plays a large role in improving the adhesive strength of the interior material of the present invention, particularly, the heat creep resistance, but the metal other than the above cannot sufficiently improve the adhesive strength. Among the components (B), preferred are sodium stearate, sodium oleate, calcium oleate, and metal salts of high molecular carboxylic acids generally referred to as ionomers (eg, ethylene- (meth) acrylic acid copolymers). Partially neutralized with a sodium compound or a zinc compound). As the component (B), not only one kind may be used alone, but two or more kinds may be used in combination.

The mixing ratio of the components (A) and (B) is not particularly limited, and includes, for example, the manufacturing conditions and performance required for the interior material of the present invention, such as the type of the base material to be bonded and the bonding process. The ratio can be set arbitrarily according to the use of the obtained interior material. Generally, the ratio of the number of moles of metal atoms in the component (B) to the number of moles of units derived from the radically polymerizable acid anhydride in the component (A) is 1/10 to 10/1.
, Preferably in the range of 2/10 to 10/2, and more preferably in the range of 3/10 to 10/3.
The thermoplastic resin composition prepared at this mixing ratio exhibits good adhesiveness and gives the interior material of the present invention excellent adhesive strength. Especially when manufacturing laminates used as interior materials for automobiles, etc., since the skin material and the substrate material can be strongly bonded at a low temperature, damage to the skin material can be prevented, and the heat creep resistance is excellent. Thus, the interior material can be obtained. In the case of special applications, for example, when adhesion at a very low temperature (about 90 ° C.) is required, the compounding ratio can be outside the above range.

[0011] The thermoplastic resin composition constituting the adhesive layer of the interior material of the present invention contains the above-mentioned component (A) and component (B).
In addition to the components, various additives, compounding agents, fillers, and the like can be compounded as long as the characteristics of the interior material of the present invention are not impaired. Specifically, for example, inorganic materials such as antioxidants (heat stabilizers), ultraviolet absorbers (light stabilizers), antistatic agents, antifogging agents, flame retardants, lubricants (slip agents, antiblocking agents), and glass fillers Examples include fillers, organic fillers, reinforcing agents, coloring agents (dyes and pigments), foaming agents, crosslinking agents, and fragrances. These additives and the like may be added when the resin composition of the present invention is produced, or may be added to the component (A) or the component (B) from the beginning.

The above thermoplastic resin composition is prepared by mixing the components (A) and (B), and if necessary, other components. In mixing the components, various commonly known methods can be used. Specifically, for example, a method of dissolving and reprecipitating each component in a solvent such as high-temperature toluene, and a method of mixing each component in a molten state, that is, a commonly used pressure kneader, roll, Banbury Examples thereof include a method using a mixer, a static mixer, a screw type extruder, and the like. In some cases, each component may be dry blended to form a composition at the time of molding. That is, the respective components can be mixed in the form of pellets or powder, and can be melt-mixed using the production stage of a film or the like.

The interior material of the present invention uses a skin material and a substrate material as a base material, and is particularly required for automobiles and dwellings which are required to have adhesive strength when bonded at low temperature and heat creep resistance at high temperature. It can be suitably used as an interior material such as. Here, there are no particular restrictions on the skin material and the substrate material that can be used.
The present invention can be applied to various materials used for interior materials such as houses. For example, as a skin material, polyester non-woven fabric, brushed knit, fabric, suede-like synthetic leather, vinyl chloride (PVC) leather, polyurethane leather, polypropylene-based thermoplastic elastomer, or urethane foam to provide cushioning properties, foamed urethane, foamed foam What bonded together foams, such as polypropylene, polyethylene foam, and polyvinylidene foam, is mentioned. On the other hand, examples of the substrate material include resin felt, a phenol resin plate containing glass fibers, corrugated cardboard, polypropylene honeycomb, polystyrene foam, or a material obtained by bonding a nonwoven fabric to any of these materials.

In the case of manufacturing the above-mentioned interior material, various conventionally known molding methods can be applied. For example,
Heat the substrate material to a predetermined temperature, set it in a vacuum forming machine,
A method in which the thermoplastic resin composition formed into a film by inflation molding or T-die molding or the like is placed thereon, and a skin material heated to a predetermined temperature in advance is vacuum-pressed; between the skin material and the substrate material A method in which the above film is sandwiched and hot-pressed; the adhesive layer side of the laminate obtained by extruding the thermoplastic resin composition on the skin material by extrusion laminating, and further hot-pressing or hot-rolling the substrate material A method of thermocompression bonding; powdering the thermoplastic resin composition and sprinkling it on a substrate material placed on a hot press;
A method of hot-pressing the skin material thereon; and a method of hot-pressing or hot-pressing a laminate obtained by previously laminating the above film on the adhesive side of the skin material with a hot roll or a hot roll to a substrate material. And the like.

[0015]

EXAMPLES The present invention will be specifically described with reference to Reference Examples, Comparative Reference Examples, Examples and Comparative Examples. Reference Example 1 As an ethylene-based multi-component copolymer (A), an ethylene-maleic anhydride-methyl methacrylate terpolymer was used. This terpolymer was prepared using a high-pressure low-density polyethylene plant at a polymerization temperature of 240 ° C and a polymerization pressure of 1,9.
It was manufactured under the condition of 00 kg / cm ² . The MFR of this terpolymer (JIS-K7210, 190 ° C, hereinafter MF
R uses this condition. ) Was 15 g / 10 min, the ratio of units derived from maleic anhydride was 2.2% by weight, and the ratio of units derived from methyl methacrylate was 16% by weight. In addition, the composition of the comonomer was determined by an infrared absorption spectrum. On the other hand, as the metal salt (B) of the organic carboxylic acid, an ionomer (a) was used. This ionomer (a) is obtained by mixing a copolymer of ethylene and methacrylic acid (methacrylic acid content: 20% by weight) with water / methanol = 1/1.
Treated with sodium acetate for 2 hours at 50 ° C. in a solvent of 55 ° C. to obtain 55 units of units derived from methacrylic acid in the copolymer.
It is a partially neutralized product obtained by neutralizing mol%. The MF
R was 2.8 g / 10 minutes. The weight ratio ((A) / (B)) of the two components was 85/15, and 0.2% by weight of magnesium silicate and erucic acid as additives were added to the total amount of the components (A) and (B). After dry blending 0.2% by weight of amide with a tumbler, the mixture was melt-kneaded at 180 ° C. using a 37 mmφ co-rotating twin screw extruder to obtain resin composition pellets. The contents of this formulation are shown in Table 1.

Comparative Reference Example 1 The procedure of Reference Example 1 was repeated, except that the ionomer (a) was not used, to obtain a pellet of the resin composition. The contents of this formulation are shown in Table 1.

Comparative Reference Example 2 A pellet of a resin composition was obtained in the same manner as in Reference Example 1, except that an ethylene-methyl acrylate binary copolymer was used as the component (A). The contents of this formulation are shown in Table 1.

Reference Examples 2 to 7 Various ethylene-based multi-component copolymers (A) were produced in the same manner as in Reference Example 1, and various kinds of metal salts of organic carboxylic acids (B) were also prepared. Various resin compositions shown as Reference Examples 2 to 7 were prepared. The composition is shown in Table 1.

[0019]

[Table 1]

[0020]

[Table 2]

Example 1 The pellets obtained in Reference Example 1 were formed into a film having a thickness of 75 μm with an inflation film forming machine having an extruder having a diameter of 45 mm, and a cylindrical film was cut.
A 0 cm wide film was obtained. Using this film as an adhesive layer, substrates (skin material and substrate material) actually used for automotive interior materials were adhered, and the adhesion was tested. Skin material is polyethylene terephthalate (PET)
Resin felt (RF) was used for the base nonwoven fabric and the substrate material.
Adhesion was performed by sandwiching the skin material, the above-mentioned film, and the substrate material in this order from above on a hot press set at 110 ° C. on the upper plate and 140 ° C. on the lower plate, and pressure-bonded at a substantial surface pressure of 2 kg / cm ² for 30 seconds. The size of the press of the substrate material was 150 mm × 175 mm according to JIS-K6829. After bonding, 23
25m after conditioning for 24 hours at 50 ℃ and 50% relative humidity
m width of the test piece, and using a tensile tester at room temperature (23 ° C.).
C.) and a 180 ° peel test at high temperature (85 ° C.). In principle, adhesive strength at peeling (g / 25mm)
When the skin material or the substrate material was broken before peeling, the strength at the time of breaking was measured. Further, a load of 100 g was hung on the test piece which was peeled partway, and the peel distance (mm) when left in an atmosphere of 80 ° C. for 24 hours was measured, and this was used as a measure of heat creep resistance. The value of the adhesive strength is the average value of five test pieces (maximum, minimum two-point cut), and the heat creep resistance is the average value of three test pieces. The results are shown in Table 2.

Examples 2 to 4 As shown in Table 2, the same operation as in Example 1 was carried out except that the types of the resin composition for the adhesive layer, the skin material and the substrate material were changed. The results are shown in Table 2.

Example 5 The film obtained in Example 1 was used, and 0.2 was used as a skin material.
2 mm foamed polypropylene (PP) with vinyl chloride resin leather of 2 mm, resin felt (R
F) was used to test the adhesion. First, the skin and the film were sandwiched by a Teflon coat roll heated to 130 ° C., and a hot roll laminating treatment was performed at a speed of 5 m / min. Next, the substrate material is brought to 80 ° C.
After heating for 1 minute, the epidermis was heated to 120 ° C. and bonded by a vacuum bonding method. The results are shown in Table 2.

Examples 6 to 8 As shown in Table 2, the same operation as in Example 5 was carried out except that the types of the resin composition for the adhesive layer, the skin material and the substrate material were changed. The results are shown in Table 2.

Comparative Examples 1 to 4 Films were produced from the pellets obtained in Comparative Reference Example 1 in the same manner as in Example 1. This film was used as an adhesive layer, and the operation was performed in the same manner as in Example 1 except that the types of the skin material and the substrate material were changed as shown in Table 2. Second result
It is shown in the table.

Comparative Examples 5 to 8 Films were produced from the pellets obtained in Comparative Reference Example 2 in the same manner as in Example 1. This film was used as an adhesive layer, and the operation was performed in the same manner as in Example 1 except that the types of the skin material and the substrate material were changed as shown in Table 2. Second result
It is shown in the table.

The results of the above test are shown in Table 2. Example 1
In the case of the laminates of Nos. To 8, the adhesive strength at normal temperature and high temperature and the heat creep resistance were all good. Also, the bonding operation was very easy and sanitary, and the workability was good. That is, the laminate of the present invention can be widely used in various fields, and can be particularly suitably used as an interior material for automobiles and the like. Further, the laminate of the present invention can maintain the surface of the laminate material without damaging the pattern peculiar to the vinyl chloride resin leather even when the skin material to which the vinyl chloride resin leather is pasted (Examples 5 to 8) is used. Can be used widely without inviting. On the other hand, Comparative Example 1
In the case of the laminates of Nos. 1 to 4, the adhesive strength was relatively good, but the heat creep resistance was significantly inferior, and there was a large problem in using them as interior materials for automobiles and the like. In addition, in the case of the laminates of Comparative Examples 5 to 8, before the measurement of the heat creep resistance, the adhesive strength was completely insufficient, and a laminate that could withstand practical use could not be obtained.

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

As described above, the interior material of the present invention comprises:
It has excellent adhesive strength at room temperature and high temperature, and can be widely used in various fields. Particularly, since the adhesive strength is excellent when the base material is bonded at a low temperature, the skin material can be prevented from being damaged during the manufacturing process, and the heat-resistant creep property is excellent. It can be suitably used as an interior material such as. Moreover, in the case of manufacturing the interior material of the present invention, it is not necessary to use an organic solvent when laminating the adhesive layer or bonding the base material layer,
Further, since the working process is simple, there is no problem in the manufacturing process. Furthermore, since the thermoplastic resin composition used for the adhesive layer of the interior material of the present invention can be manufactured using the same method and equipment as the conventional adhesive resin, it can be manufactured relatively inexpensively and easily. Can be. Therefore, the interior material of the present invention is effectively used especially as an interior material for automobiles, dwellings, and the like.

Continuation of the front page (72) Inventor Hirotaka Tagoshi 2nd Nakanosu, Oita-shi, Oita Prefecture Showa Denko KK Oita Research Laboratory (56) References JP-A-2-235743 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) B32B 1/00-35/00

Claims (1)

(57) [Claims] 1. A laminate comprising a skin material adhered to a substrate material via an adhesive layer, wherein the adhesive material layer is composed of (A) ethylene, a radical polymerizable acid anhydride and another radical polymerizable comonomer. Wherein the proportion of units derived from the radical polymerizable acid anhydride in the ethylene-based multi-component copolymer is 0.1 to 5% by weight and is derived from other radical polymerizable comonomers. 3-50% by weight of unit
And a thermoplastic resin composition containing (B) a salt of an organic carboxylic acid with a metal belonging to Group IA, IIA or IIB of the periodic table. .