JPH0321202A - Face fastener forming body and its manufacture - Google Patents

Abstract

PURPOSE:To obtain a surface fastener excellent in pliability, tear resistance, and repeated disengaging and engaging ability by using soft thermoplastic resin composite composed of thermoplastic resin and vinyl aromatic group compound- conjugated diene block copolymer hydrate. CONSTITUTION:As a raw material, there is used thermoplastic resin composite composed of 95 to 40wt.% of thermoplastic resin having a decrystallizing temperature or a glass transition temperature of higher than 100 deg.C and 5 to 60wt.% of vinyl aromatic resin compound-conjugated diene block copolymer hydrate. The raw material resin is melted by heating and kneaded in an extruder 1, and is then extruded from an extrusion die 2. Then it is cooled by a cooling and sizing device 7 so as to form rib support columns 5 and rib heads 6 in the longitudinal direction of a sheet-like base section 4. Then it is led to support roll 8 and is slit (11) by a cutting blade of a cutter 9 in the support columns 5 and the rib heads 6, longitudinally, thereof so as to obtain discontinuous ribs 6'. A forming body 3' is stretched longitudinally in a stretching tank 13, and accordingly, it is turned into a face fastener forming body 3'' having the ribs 6' which are formed in intervals on the base section 4' and having a high engageability.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a hook-and-loop fastener having excellent flexibility, tearability, and repeated attachment/detachability, and a method for manufacturing the same. (Prior art) In industries such as the automobile and home appliance industries, when assembling molded bodies together, screwing with screws, etc., or specially processing the molded bodies and fitting them in, etc., were carried out, but in recent years the process has been simplified. Adhesion using double-sided adhesives or hook-and-loop fasteners is increasingly being used to reduce work time. For example, an automobile seat or the like has a structure in which a cushion body is covered with a skin material, and the seat surface is sometimes formed into a concave shape in order to maintain a sitting posture or for decoration.

When making such a seat, in order to prevent the upholstery material from lifting up from the cushion body at the recessed portions, a hook-and-loop fastener is attached to the back of the upholstery material, and a foam molded product with hook-and-loop fasteners attached to the recessed portions is also used. It is being used as a cushion body to prevent the surface material from lifting up by engaging both of the retaining parts with each other.

In addition to these uses, hook-and-loop fasteners made of polyamide elastomer, polyolefin, polyester elastomer, etc. are used for various purposes, but these hook-and-loop fasteners have good tearability, but are flexible and suffer from repeated release. Because of its poor nutritional properties, it cannot be used in locations that have complex shapes and undergo repeated deformation as described above.

(Problems to be Solved by the Invention) An object of the present invention is to obtain a hook-and-loop fastener that is excellent in flexibility, tearability, and repeated attachment/detachability.

(Means for Solving the Problems) The present invention provides a hook-and-loop fastener using a flexible thermoplastic resin material consisting of a thermoplastic resin and a hydrogenated vinyl aromatic compound to a conjugated diene block copolymer. It is characterized by this. That is, the present invention provides (.1) a thermoplastic resin 95-40 having a crystal melting temperature (Tm) or glass transition temperature (Tg) of 100°C or higher;
Weight% (2) It has at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and the content of the vinyl aromatic compound is Hydrogenated block copolymers (hereinafter referred to as hydrogenated block copolymers) obtained by hydrogenating a block copolymer in a range of 5 to 75% and hydrogenating 35% or more of aliphatic double bonds based on conjugated dienes. Vinyl aromatic compound ~ sometimes abbreviated as conjugated diene block copolymer hydrogenated product) 5
By using a thermoplastic resin composite consisting of ~60% by weight, a hook-and-loop fastener having flexibility, tearability, and repeatable detachability is provided. The thermoplastic resin used in the present invention is characterized by the heat resistance of the composition,
This is important for maintaining stiffness and stretchability. For this reason, the crystalline melting temperature (Tm) or glass transition temperature (Tg) of the thermoplastic resin needs to be 100° C. or higher. It can be used suitably. As a thermoplastic resin,
Polyethylene, polypropylene, polyolefin resins consisting of copolymers of propylene and α-olefins such as ethylene or l-butene, polystyrene, high impact polystyrene, styrene resins such as ABS, As, polyethylene terephthalate, polybutylene terephthalate polyester resins such as, polyamide resins such as nylon-6, nylon-66, nylon-12,
Polycarbonate resins, polyphenylene ether resins, and the like can be used, but polyolefin resins, particularly polypropylene and block copolymers of propylene and ethylene, are particularly preferred.

The amount of thermoplastic resin used is in the range of 95 to 40% by weight of the composition. If it exceeds 95% by weight, the resulting hook-and-loop fastener lacks flexibility and repeatable attachment/detachability, and the resulting hook-and-loop fastener is susceptible to the growth of tear scratches from defective areas in the stitched or stacked areas.

Furthermore, if the amount is less than 40% by weight, the heat resistance of the shaped article will be poor and it will be more likely to be deformed by heating. Furthermore, the problem that it is difficult to maintain the shape after stretching tends to occur. A particularly preferred amount of thermoplastic resin used is in the range of 90 to 50% by weight.

Further, the vinyl aromatic compound-conjugated diene block copolymer hydrogenated product used in the present invention is a polymer mainly composed of at least one polymer block A mainly composed of a vinyl aromatic compound and a conjugated diene compound. It has at least one block B, and the content of vinyl aromatic compound is 5 to 5.
It is a polymer obtained by hydrogenating a block copolymer in the range of 75% by weight and hydrogenating 35% or more of the aliphatic double bonds based on the conjugated diene, and the amount used is 5 to 60% of the composition. % by weight.

The structure of the block copolymer used here may be either linear or branched, and some examples are expressed as the following general formulas.

A- (B-A). , (A-B) ,,,B- (
A-B). All n≧1A-B-X-B
-A B-A-X-A-BB-A A-B B-A A-I3 A-B-X-B-A B-A-X-A-BB-A
AB Among these block copolymers, those having an A-B-A or A-B type structure are preferably used in the present invention from the viewpoint of ease of manual operation.

These block copolymers are obtained by anionic polymerization in a hydrocarbon solvent using an organic lithium compound or metallic sodium as an initiator.

Examples of hydrocarbon solvents include aliphatic hydrocarbons such as butane, pentane, n-hexane, isopentane, heptane, and octane, alicyclic hydrocarbons such as cyclobentane, methylcyclobentane, cyclohexane, and methylcyclohexane, or benzene, toluene, and xylene. Aromatic hydrocarbons such as

Examples of organic lithium compounds include ethyllithium,
n-probyllithium, n-butyllithium, sec-
Examples include butyllithium, ter L-butyllithium, hexamethylene dilithium, and the like.

In the above general formula, X in the block copolymer formula having a branched structure represents a so-called coupling agent residue.

Examples of the coupling agent include tin halide.

The content of vinyl aromatic compounds in the hydrogenated block copolymer used in the present invention ranges from 5 to 75% by weight. If the content of the vinyl aromatic compound is less than 5% by weight, the resulting hook-and-loop fastener cannot maintain its heat resistance and stiffness. When the content of vinyl aromatic compounds is 75% by weight or more,
The obtained hook-and-loop fastener tends to have problems such as lack of flexibility and poor repeatability. The preferred vinyl aromatic compound content ranges from 10 to 65% by weight. 2 Vinyl aromatic hydrocarbons referred to in the present invention include styrene, α-methylstyrene, 0, m- and p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene,
Examples include vinylanthracene, and styrene or α-methylstyrene is generally used. In addition, conjugated dienes include 1,3-butadiene, isoprene, 2
．． 3-dimethyl-1,3-7'tadiene, l,3-pentadiene, 1,3-hexadiene, etc., and 1,3-
Butadiene and isoprene are commonly used.

In the hydrogenated block copolymer used in the present invention, 35% or more of the aliphatic double bonds based on conjugated double bonds must be hydrogenated.

If the hydrogenation rate is 35% or less, thermal deterioration is likely to occur during melt mixing with the thermoplastic resin, and the weather resistance of the resulting sheet fastener is also problematic. Furthermore, they may have poor affinity with thermoplastic resins, and they also have the disadvantage that they tend to bleed more easily than molded bodies.

The hydrogenation reaction can be carried out using a noble metal-based catalyst such as platinum or palladium, Raney nickel, an organic nickel compound, an organic cobalt compound, or a composite catalyst of these compounds and other organic metal compounds.

The hydrogenation rate can be calculated by the iodine number measurement method. The amount of hydrogenated block copolymer used in the thermoplastic resin compound used in the present invention is in the range of 5 to 60% by weight. If the amount of the hydrogenated block co-vertical is outside this range, the resulting hook-and-loop fastener will have poor flexibility and repeated attachment/detachability, and will be prone to scratches, tear growth from defective areas such as stitched or stamped areas. There are problems. If the amount of hydrogenated block copolymer used exceeds this range, the heat resistance of the carved product will be poor and it will be more likely to be deformed by heating. Furthermore, the problem that it is difficult to maintain the shape after stretching tends to occur.

The thermoplastic resin composition used in the present invention essentially contains a thermoplastic resin and a hydrogenated block copolymer as described above, but may also contain paraffinic oil or naphthenic oil as necessary. By adding a so-called mineral oil-based softener, it is possible to improve fluidity during forming and give flexibility to the composition. In addition, inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, barium clay sulfate, and magnesium carbonate can be mixed for the purpose of improving the heat resistance, weather resistance, or increasing the mass of the composition. ．．
Furthermore, it is also possible to mix inorganic or organic fibrous materials such as glass fiber and carbon fiber depending on the purpose. In addition, heat stabilizers, antioxidants, light stabilizers, flame retardants, tackifiers, antistatic agents, foaming agents, etc. may be added to the thermoplastic resin composition that is the raw material resin for the hook-and-loop fastener used in the present invention. It is possible. The thermoplastic resin used in the present invention is produced by heating and melting raw materials in a mixer or mixer such as a single-screw extruder, two-wheel extruder, Banbury ξ-kisser, Brabender, Henschel ξ-kisser, oven roll, kneader, etc. Obtained by kneading.

The hook-and-loop fastener of the present invention can be obtained by melting and shaping the above assembly. The melt molding method is exemplified. In particular, extruded kaikata is particularly effective. A typical example of extrusion molding is, for example, Japanese Patent Publication No. 48-2276
It is explained in detail in Publication No. 8 and Japanese Patent Publication No. 53-22889. An overview of these will be explained using drawings (Figures 1 to 4). FIG. 1 shows an outline of the manufacturing equipment, in which raw resin is heated, melted and kneaded in an extrusion device 1, and the molten polymer is supplied to a continuous profile extrusion die 2. The molded body 3 extruded from the extrusion die 2 is cooled by the cooling sizing device 7, and then
As shown in the figure, a rib support 5 and a rib head 6 are formed which are continuous in the longitudinal direction of a sheet-like base material portion 4. The continuous irregular shaped body raw fabric 3 thus obtained is guided to a support roll 8, and as shown in FIG. is applied to form the discontinuous rib 6'. The formed body 3' which has been subjected to the incision processing is sent to a pre-stretching fixed-length roll l2, and after stretching is stretched in the longitudinal direction generally by 1.5 to 3.5 times in a stretching tank l3 between the fixed-length roll l4. As shown in the perspective view of FIG. 4, an engaging hook-and-loop fastener molded body 3# having spaced apart lips 6' on the stretched base member 4' is obtained. Further, the molded body 3# is subjected to post-processing such as heat setting treatment and coating treatment as necessary. (Examples) In order to explain the present invention more specifically and in detail, Examples of the present invention are shown below, but the content of the present invention is not limited to these Examples. The performance evaluation of the hook-and-loop fastener was based on the method shown below. a) Flexibility Mechanical properties were measured using a method compliant with JIS K-7113, and a comprehensive evaluation was performed using the initial Young's modulus value and the hardness value using a method compliant with JIS K-7215 as indicators of flexibility. .

b) Tearability The tear strength of the hook-and-loop fastener was measured by a method based on JIS K-6301-9.2 and used as an index of tearability.

C) Repeated removability A pile base fabric with a specific structure and this hook-and-loop fastener are
The procedure of laminating with a roll with a load of kg/am and then peeling was repeated 500 times, and the retention rate of the peeling strength at that time with respect to the initial peeling strength was determined, and according to the criteria shown below. evaluated.

Peel strength retention rating: 70% or more Good (◎) 55-69% Fair (○) 45-54%
Slightly inferior (△〉 44% or less Poor (×) d) Heat resistance (11 Heat deformation performance) The shrinkage rate and The crystal melting temperature was measured using a differential scanning calorimeter (DSC), and these values were used as an index of thermal deformation performance.

(2) Heat aging performance The hook-and-loop fastener was placed in an air oven at 120°C for 24 hours, then taken out, and when cooled to room temperature, the stickiness of the fastener surface was determined by touch and was used as an index of heat aging performance.

Based on the evaluation results of heat deformation performance and heat aging performance, we conducted a comprehensive evaluation of the heat resistance of hook and loop fasteners. In addition, the display in Table 1 is ◎
: Good, ○: f times, Δ: Slightly poor, ×: Inferior.

Example 1 3,000 parts by weight of cyclohexane, 50 parts by weight of sufficiently dehydrated styrene, and 0.7 parts by weight of n-butyllithium were added to a pressure-resistant container equipped with a stirring device, polymerized at 60°C for 60 minutes, and then 300 parts by weight of isobrene was added. for 60 minutes.
Next, 50 parts by weight of styrene was added and polymerized for 60 minutes to form a styrene-isoprene-styrene type block copolymer. The obtained block copolymer had a styrene content of 25% by weight and a number average molecular weight of 120,000. Cyclohexane was added to this polymer solution so that the polymer concentration was 10% by weight, degassed under reduced pressure, replaced with hydrogen, and further 0.0% by weight. 5
A hydrogenation reaction was carried out in a hydrogen atmosphere of 10 kg/1 by adding a palladium catalyst of weight%/polymer, and the hydrogenation rate was 97%.
A hydrogenated block copolymer was obtained. 70 parts by weight of commercially available polypropylene was added to 30 parts by weight of this hydrogenated block copolymer and melt-kneaded using a small twin-screw extruder to prepare a pellet compound. Using the obtained Beresoto compound, a hook-and-loop fastener was made using the apparatus shown in FIG. 1 in the following manner.

First, using an axle extruder (full flight screw, L/D = 24) with a diameter of 401 m, the cylinder temperature was 225 m.
Extruded under the following conditions: ℃, profile temperature 220℃, extrusion rate 8 kg/Hr, profile extrusion speed 2.8 m/IIlin,
The heteromorphic body material is shaped at a cooling water temperature of 60°C. Next, in the cutting process, the lip part was cut into a 0.4** pinch, then stretched 2.5 times at a stretching temperature of 115°C, and further heat-scented at a line speed of 7 m/min to obtain the shape shown in Figure 4. I got a hook-and-loop fastener.

The dimensions of each part of the hook-and-loop fastener are as follows.

Base material width = 351l Thickness: Pi-notch of ribs spaced apart by 0.3m: 1.7mm Number of rib rows
: Shape of 7 row ribs : Support width
: 0.5m Pillar thickness: 0.4mm Rib height: 1.7m Rib head width: 1.5mm The performance of the obtained hook-and-loop fastener was evaluated, and the results were
Shown in the table. The workability in these processing steps was visually determined by comparing the flow performance of the molten polymer to the details of the nozzle during extrusion from the irregularly shaped nozzle and the uniform stretchability in the drawing step.

Comparative Example 1 Except that the thermoplastic resin used was commercially available polypropylene,
A hook-and-loop fastener was manufactured in the same manner as in Example 1, and its performance was evaluated. The results are shown in Table 1, and polypropylene alone is not preferred because it has poor flexibility, tear strength, and repeated removability. Example 2.3 Polybropylene/hydrogenated block copolymer mixing weight ratio is 5
Hook-and-loop fasteners were produced in the same manner as in Example 1, except that they were 0/50 (Example 2) or 92/8 (Example 3), and their performance was evaluated.The results are shown in Table 1. ．From this result, the physical properties of the hook and loop fastener change depending on the amount of hydrogenated block copolymer added, but it is within a range that can be used for practical purposes. Comparative Examples 2 and 3 Polypropylene/Hydrogenated Block Copolymer Mixture Weight ratio is 3
Hook-and-loop fasteners were produced in the same manner as in Example 1, except that they were 5/65 (Comparative Example 2) or 97/3 (Comparative Example 3), and their performance was evaluated. The results are shown in Table 1. These results show that if the amount of hydrogenated block copolymer added is too large, the processability will decrease and the shrinkage rate due to heating will also be large, which is not preferable.

On the other hand, if the amount added is too small, flexibility and repeated desorption properties will deteriorate, which is not preferable.

Hook-and-loop fasteners were produced in the same manner as in Example 1, except that the weight percentage was 8% by weight (Example 4) or 8% by weight (Example 5), and their performance was evaluated.The results are shown in Table 1. From this result, when the styrene content is high, the flexibility and repeated desorption performance are slightly inferior to those of Example 1, but the performance is sufficient for practical use.In addition, when the styrene content is low, the repeated desorption performance is lower than that of Example 1. Although the elasticity and thermal deformability are inferior, the performance is sufficient for practical purposes. The results are shown in Table 1.The results show that if the styrene content is too high, the flexibility and repeated detachability will be poor, causing practical problems. If it is too small, the repeatability and heat deformability will be poor and it cannot be used practically.

manufactured a hook-and-loop fastener in the same manner as in Example 1 and evaluated its performance. The results are shown in Table 1. From this result, when the hydrogenation rate is lowered, the heat aging resistance is slightly inferior to that of Example 1, but the performance is sufficient for practical use.

It's not good. Furthermore, the repeatability of attaching and detaching is also somewhat poor. (c) Effects of the present invention) The stylish hook-and-loop fastener using the thermoplastic resin composition of the present invention is characterized by excellent flexibility, tearability, and repeated removability without reducing strength or heat resistance. In particular, the tearability of the base material is significantly improved when the manufacturing method involves stretching the base material. In addition, when manufacturing hook-and-loop fasteners using the thermoplastic resin composite of the present invention, the shapeability such as extrudability and stretchability is good, making it possible to stabilize and speed up the manufacturing process and reduce manufacturing costs. vinegar! ，
:． ．． A is 7''. The blank below is a hook-and-loop fastener manufactured in the same manner as in Example 1, and its performance was evaluated. The results are shown in Table 1. This result shows that if the hydrogenation rate is too low, there will be slight deterioration during profile extrusion, and the heat aging resistance will be significantly poor for practical use.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram of a manufacturing apparatus for manufacturing the hook-and-loop fastener of the present invention, Fig. 2 is a partial perspective view of a continuous isomerically molded raw material, Fig. 3 is a side view showing the incision processing process, and Fig. 4 is a diagram of the invention. It is a perspective view showing the hook-and-loop fastener molded object. 1... Extrusion device, 2... Deformed extrusion goo, 3...
Continuous irregularly shaped body raw material, 3'... Incised shaped body, 3#... Hook and loop fastener formed body, 4... Base material part,
4'... Stretched base material portion, 5... Rib support, 6...
... Rib head, 6'... Discontinuous rib, 7... Cooling sizing device, 8... Support roll, 9... Cutting machine,
10... Cutting blade, 1l... Cut processing line, 12.
・・Pre-stretching constant length roll, 13 ・・Stretching tank, 14...
Fixed length roll after stretching.

Claims (3)

[Claims] (1) (a) 95 to 40% by weight of a thermoplastic resin having at least one of crystalline melting temperature (Tm) or glass transition temperature (Tg) of 100°C or higher, and (b) a polymer mainly composed of a vinyl aromatic compound A block copolymer having at least one block A and at least one polymer block B mainly composed of a conjugated diene compound and having a vinyl aromatic compound content in the range of 5 to 75% by weight is hydrogenated. A surface fastener molded article comprising a thermoplastic resin composition comprising 5 to 60% by weight of a hydrogenated block copolymer obtained by adding hydrogen to 35% or more of the aliphatic double bonds based on a conjugated diene. (2) (a) Thermoplastic resin 95~ having a crystalline melting temperature (Tm) or glass transition temperature (Tg) of 100°C or higher
40% by weight and (b) has at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and contains a vinyl aromatic compound. Hydrogenated block copolymer 5-60% by weight obtained by hydrogenating a block copolymer having an amount in the range of 5-75% by weight and hydrogenating 35% or more of the aliphatic double bonds based on the conjugated diene. A method for producing a hook-and-loop fastener forming body, comprising melt-molding a thermoplastic resin composition consisting of %. (3) (a) Thermoplastic resin 95~ having a crystalline melting temperature (Tm) or glass transition temperature (Tg) of 100°C or higher
40% by weight and (b) has at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and contains a vinyl aromatic compound. Hydrogenated block copolymer 5 obtained by hydrogenating a block copolymer having an amount in the range of 5 to 75% by weight, and hydrogenating 35% or more of the aliphatic double bonds based on the conjugated double bonds. 1. A method for producing a surface fastener molded article, which comprises extruding a thermoplastic resin composition containing 60% by weight and stretching the thermoplastic resin composition as necessary.