JPH04353437A - Electrostatically flocked product - Google Patents

Abstract

PURPOSE:To provide an electrostatically flocked product capable of retaining the wear resistance of a flocked part for a longer period of time than the conventional product, responding to the need for an improved durability. CONSTITUTION:In an electrostatically flocked product wherein electrostatically flocked parts 3A and 3B are formed on the base material 1 consisting of a high-molecular elastic material via an adhesive layer and treated with the urethane coating compositions having a nonreactive silicone oil added thereto, the urethane coating compositions are characterized by having three components, i.e., hydroxyl prepolymer, a nonreactive silicone oil and polyisocyanate contained therein as a curing agent, a siloxane structure being introduced into the main chain of the hydroxyl prepolymer.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to electrostatic flocking products. In particular, electrostatic capacitors for automobiles that require excellent abrasion resistance and other physical properties (water repellency, soundproofing, non-freezing, non-sticking properties, etc.) on the flocked part for a long period of time under harsh conditions such as outdoors. This invention is suitable for flocked glass orchids. Here, Figure 1
Electrostatic flocked glass run for automobiles (hereinafter simply "
It's called "Glass Run." ) will be used as an example, but the invention is not limited to this.

[0002] Below is a list of abbreviations for compounds and polymers whose explanations are omitted in this specification.

■Diisocyanate MDI...4.4'-diphenylmethane diisocyanate, TDI...tolylene diisocyanate, ■Polymer NBR...nitrile rubber, EPDM...ethylene propylene diene terpolymer, C
R...Chloroprene rubber, PVC...Polyvinyl chloride In addition, in the following explanation, compounding units are as follows, unless otherwise specified.
It is a unit of weight.

0004

2. Description of the Related Art The flocked portions 3A and 3B of the above-mentioned type of glass run 1 (attached to the run channel 2), particularly the flocked portion 3A of the groove bottom 5, are in contact with the end of the window glass 9. Compared to the flocked parts 3B of the seal lip part 7, the flocked parts 3A and 3B have a higher frictional resistance and are easily deteriorated because they are used outdoors for a long time.

[0005] For this reason, the abrasion resistance of the flocked portions 3A and 3B deteriorates over time, causing a hair loss phenomenon, and the sliding resistance of the glass rapidly increases, and in extreme cases, the glass becomes unable to slide.

[0006] In order to improve the abrasion resistance of this flocked part, a urethane prepolymer having an isocyanate group at the end (
The flocked area 3A is coated with a coating composition containing a specific amount of non-reactive silicone oil in an isocyanate urethane prepolymer.
Glass run with 3B coated (electrostatic flocking product)
has been proposed by one of the applicants (Japanese Patent Publication No. 62
-15334).

[0007] This electrostatic flocking product was able to maintain good abrasion resistance for a considerable period of time even under severe usage conditions.

[0008]

[Problems to be Solved by the Invention] However, in recent years, there has been a growing demand for improved durability of the flocked portion of glass runs under severe usage conditions.

[0009] In view of the above, an object of the present invention is to provide an electrostatic flocking product that can maintain the wear resistance of the flocked portion for a longer period of time than before and that can meet the demand for improved durability. It is about providing.

0010

[Means for Solving the Problems] The present invention solves the above problems with the following configuration.

[0011] An electrostatic flocked part is formed on a base material made of an elastic polymeric material via an adhesive layer, and the electrostatic flocked part is made of a urethane-based paint composition containing non-reactive silicone oil. In the electrostatic flocking product treated with a coating film, the urethane-based coating composition is composed of three components: a hydroxyl prepolymer, a non-reactive silicone oil, and a polyisocyanate as a curing agent. The polymer is characterized by having a siloxane structure introduced into the main chain.

0012

[Detailed explanation of means]

Each means of the present invention will be explained in detail below.

(i) In the electrostatic flocking product of the present invention, an electrostatic flocking part is formed on a base material made of an elastic polymeric material via an adhesive layer, and the electrostatic flocking part is made of non-reactive silicone. The first requirement (prerequisite requirement) is that the coating be treated with a urethane paint composition containing oil.

■The above-mentioned elastic polymer material is EPDM.
Synthetic rubbers such as , CR, PVC/NBR, and thermoplastic elastomers such as PVC, polyolefin, polyester, and urethane can be used.

(2) The base material is molded by extrusion, transfer molding, injection molding, compression molding, etc. using the above-mentioned elastic polymer material.

■Usually urethane adhesive is used,
A one-component type (polyisocyanate type, isocyanate prepolymer type, etc.) or a two-component type (polyol/polyisocyanate type, hydroxyl prepolymer/polyisocyanate type, etc.) can be used. This adhesive is usually applied with a film thickness of 50 to 10 mm by spray or roller.
Coat so that the thickness is 0 μm.

(2) The electrostatic flocking section is formed using nylon pile or polyester pile using a normal electrostatic flocking device after applying the above-mentioned adhesive.

(2) The urethane coating composition containing non-reactive silicone oil is a characteristic feature of the present invention and will be described later.

(2) The coating film treatment is carried out by spray coating or drop coating. The coating amount is usually 0.02-0.05g/c
Let it be m2. If the amount is too low, the purpose of the coating film treatment will not be achieved.
If the amount is too large, the characteristics of the flocked area will be reduced and the effect of increasing the amount of application will reach saturation, leading to material waste.

(ii) In the electrostatic flocking product of the present invention, the urethane coating composition contains three components of hydroxyl prepolymer, non-reactive silicone oil, and polyisocyanate as a curing agent in a solvent. The second requirement is that it be dissolved.

(2) Hydroxyl prepolymer is a so-called urethane polyol having hydroxyl groups at both ends. Details of this hydroxyl prepolymer will be described later.

(2) Non-reactive silicone oil is a term for a reactive silicone oil in which a reactive group having active hydrogen, such as a carboxyl group, an amino group, an alkoxyl group, or a hydroxyl group, is introduced into the side chain of polysiloxane. Examples of the non-reactive silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, fluorosilicone oil, and the like.

[0023] The reason why non-reactive silicone oil is used is because if reactive silicone oil is used, most of it will chemically bond with the urethane polymer, and bleeding of the silicone oil from the urethane coating cannot be expected. be.

[0024] The blending amount of this silicone oil is 8 to 100 parts of hydroxyl prepolymer (resin content).
The amount is 250 parts (preferably 40 to 210 parts). If it is less than 8 parts, sufficient abrasion resistance cannot be obtained, and if it exceeds 250 parts, problems tend to occur in compatibility with polyurethane resins, and the urethane coating film due to poor dispersion of silicone oil tends to occur. This inhibits the adhesion of the fibers to the flocked short fibers and the adhesive layer.

(2) The amount of the curing agent (polyisocyanate) to be blended is 1 to 100 parts per 100 parts of the hydroxyl prepolymer (resin content). If it is less than 1 part, the adhesion of the urethane coating to the short flocked fibers and the adhesive layer will be poor, and if it exceeds 100 parts, the urethane coating will become hard and contribute to the generation of squeaking noise.

[0026] As the polyisocyanate, a general-purpose curing agent for urethane paints can be used, and the following can be exemplified.

Adduct polyisocyanate/polymerized polyisocyanate of pure MDI, crude MDI, polymeric MDI, TDI, isophorone diisocyanate (I
PDI), naphthalene diisocyanate, metaxylylene diisocyanate (XDI), hydrogenated MDI, hydrogenated TDI, hexamethaxylylene diisocyanate (
HXDI), etc. (2) The paint composition is adjusted to have a viscosity suitable for coating by adding carbon black and a solvent to the above-mentioned three essential components as appropriate.

[0028] Carbon black has the effect of reinforcing and coloring the coating film, and the blending amount is 100% of the resin content (prepolymer).
parts, 0.1 to 100 parts.

As the above-mentioned solvent, general-purpose urethane paint solvents can be used, and one or a suitable combination of the solvents listed below can be used.

Benzene, toluene, xylene, ethylbenzene, trichloroethylene, ethylene chloride, dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate , anisole, tetrahydrofuran, etc.'' (iii) The third requirement of the electrostatic flocking product of the present invention is that the hydroxyl prepolymer in the coating composition has siloxane introduced into its main chain. .

The synthesis of this hydroxyl prepolymer is as follows:
For example, a solvent is added to and mixed with one or more of amino-modified silicones and polyether-modified silicones, polyol, and diisocyanate, and the mixture is reacted in dry nitrogen gas at 80-130°C for 60-300 minutes. Prepare.

[0032] Here, the amount of modified silicone is 1 to 200 parts based on the polyol. If it exceeds 200 copies,
The coating film becomes brittle and does not have sufficient wear resistance. The molar ratio of isocyanate to polyol and modified silicone is 0.
．． 5 to 0.95. If it is less than 0.5, the coating film becomes brittle and sufficient abrasion resistance cannot be obtained. 0.95
If it exceeds the urethane resin, the viscosity of the urethane resin will increase, making it difficult to fit into the flocked area, impairing the texture of the flocked area, and causing squeaking noise.

[0033] Each of the above components will be explained in detail.

[0034] Amino-modified silicone: Those having amino groups at both ends, such as aminopropyl group-modified silicone, N-(β-aminoethyl), iminopropyl group-modified silicone, and aminophenoxymethyl group-modified silicone.

■Polyether modified silicone; Si-H
Those having hydroxyl groups at both ends, such as those obtained by addition reaction or dehydrogenation of dimethylpolysiloxane having groups with polyethylene glycol, polypropylene glycol, etc.

[0036] As the polyol, the following general-purpose polyester-based and polyether-based ones used in urethane paints can be used.

“Polyester polyol; polyethylene adipate (PEA), polybutylene adipate (PB
A), condensation polyester polyols such as polyethylene butylene adipate, polydiethylene adipate, polyhexamethylene adipate, polyethylene phthalate, polybutylene phthalate, lactone polyester polyols such as polycaprolactone, polycarbonate diols, etc. ” “Polyether polyol; polyoxyethylene glycol (PEG), polyoxypropylene glycol (P
PG), polytetramethylene ether glycol, etc. ``■ As the diisocyanate, an appropriate divalent one can be selected from among the above-mentioned polyisocyanates. Specifically, MDI, TDI, HTDI, IPDI, NDI,
XDI, HMDI, HXDI, etc. can be mentioned.

[0038]

Effects and Effects of the Invention The electrostatic flocking product of the present invention has the above-described structure, so that the urethane coating film strongly adheres to the flocked short fibers and the adhesive layer, and as shown in the examples below, The wear resistance of the flocked surface does not deteriorate even under harsh conditions such as hours of outdoor exposure, significantly extending the product life.

The reason why the durability is improved compared to the conventional example described in the above-mentioned publication is presumed to be as follows.

Since the main chain of the urethane resin that forms the coating film contains a siloxane structure, 1) the sliding resistance with glass is lower than that of the conventional example, and 2) the sliding resistance with non-reactive silicone oil is reduced. Miscibility is increased, and the amount of silicone oil that is lost over time is suppressed. (1) Even if most of the silicone oil is washed away from the coating film, the sliding resistance does not increase rapidly.

[0041]

[Examples/Comparative Examples] Hereinafter, in order to confirm the effects of the present invention, examples will be explained together with comparative examples and conventional examples.

A. Manufacture of glass run (i) Preparation of glass run base material: An extruded product of the following rubber compound was vulcanized at 170° C. for 5 minutes. Immediately after applying a two-component urethane paint (polyester polyol/polyisocyanate) with a roller (coating amount: 70μ) to the surface of the vulcanizate, the flocked portion was made using an electrostatic flocking device.
- Flocked with nylon pile and air dried (150℃ x 10 minutes)
It was prepared by

EPDM combination formulation EPDM
100 parts paraffin oil
90
part carbon black
190 parts calcium carbonate
30 parts zinc white
5 parts stearic acid

1 part vulcanization accelerator
3.5 parts sulfur
Part 2 (ii) Preparation of paint: To the hydroxyl prepolymer prepared under the conditions in Table 1, each silicone oil, curing agent, solvent, and carbon black were added and mixed with the composition shown in Table 2 to prepare each paint. .

(iii) Coating film treatment: Each of the above paints was spray applied to the flocked portion of the base material at a set coating amount of 0.04 g/cm 2 and dried at 150° C. for 3 minutes.

B. Wear test and evaluation of test results: (i)
Abrasion test: Using the following testing machine, under the following conditions, a normal state and after a weathering test (accelerated weathering test was performed for a predetermined time according to JIS D 0205, and measurement was performed after 24 hours of standing at room temperature).

■Testing machine...KI type abrasion tester, ■Test conditions...Abrasion element: Glass (thickness 3.5 mm), Load: 3
kg, wear element cycle: 60 times/min, wear element stroke: 14
5mm.

(ii) Evaluation of test results: If the amount of silicone oil blended is too small (Comparative Examples 1 and 2), wear resistance may be inferior to conventional examples (using non-silicone modified prepolymers). I understand. Furthermore, it can be seen that when the amount of silicone oil blended is too large (Comparative Example 3), wear resistance equivalent to that of the conventional example can only be obtained.

[0048] Compared to the above conventional examples and comparative examples, each of the examples showed that under harsh conditions such as after 1000 hours of accelerated weathering test,
It can be seen that it exhibits significantly superior wear resistance. In particular, when the silicone content is 40 parts or more (Examples 1 to 4), the wear resistance is excellent.

[0049]

[Table 1]

[0050]

[Table 2]

[Brief explanation of the drawing]

FIG. 1 is a schematic cross-sectional view showing an example of an electrostatic flocking product to which the present invention can be applied.

[Explanation of figure symbols]

1 Glass run, 3A, 3B Flocking part,

Claims (1)

[Claims] Claim 1: An electrostatic flocked part is formed on a base material made of an elastic polymeric material via an adhesive layer, and the electrostatic flocked part is made of a urethane-based paint composition containing non-reactive silicone oil. In the electrostatic flocking product which is coated with a material, the urethane coating composition is composed of three components: a hydroxyl prepolymer, a non-reactive silicone oil, and a curing agent polyisocyanate; An electrostatic flocking product characterized in that the hydroxyl prepolymer has a siloxane structure introduced into its main chain.