KR101258074B1 - Contineous slab-type polyurethane hard foams and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a slab continuous foamed rigid polyurethane foam, a method for producing the same, and an automotive part using the foam.

The polyurethane foam according to the present invention is obtained by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a blowing agent and a foam stabilizer, wherein the polyol is a trifunctional first polyether polyol 10-70 having an OH value of 10 to 100. 10 to 70% by weight of trifunctional second polyether polyol having a% by weight and OH value of 300 to 600 and 0 to 30% by weight of tetrafunctional polyether to OH-V 35 to 700, and OH-V to 300 to 600 It is made of 0 to 30% by weight of polyether of 4 to 6 functional groups, the blowing agent is characterized in that the water.

The present invention provides a rigid polyurethane suitable for the production of slab continuous molding having excellent thermal insulation and sound insulation using a polyol composition composed of polyether polyol, and provides an environmentally friendly automotive finish.

Description

Slab continuous foamed rigid polyurethane foam and its manufacturing method {CONTINEOUS SLAB-TYPE POLYURETHANE HARD FOAMS AND MANUFACTURING METHOD THEREOF}

The present invention relates to a slab continuous foamed rigid polyurethane foam, a method for producing the same, and an automotive part using the foam.

Recently, with the development of the automotive industry, the use of excellent polyurethane products in the automotive interior materials is increasing, and among them, the application amount of various kinds of interior materials having excellent sound insulation and insulation properties is increasing. Especially in case of head-liner used as a ceiling material inside a car, it should maintain the rigidity enough to maintain the interior ceiling shape of the car, and have excellent moldability to fit various shapes of the car. It should have the property of good indoor soundproofing.

Polyurethane is prepared by separately preparing a polyol solution and a polyisocyanate solution, and mixing the respective products to prepare a polyurethane foam. In general, the polyurethane is foamed by an intermittent and continuous process. An intermittent type is a product that is made of a mold and a urethane foam is put into the mold and cured after a certain time, and then used as a product by demolding.In the case of an intermittent type, both soft and hard urethane are similar. The foam form is slightly different.

Rigid continuous foaming is used where the foam grows by having two upper and lower adhered surfaces (mainly STEEL) and the foam grows and completely cures past the curing zone at a certain temperature. It consists only of the support of the lower part, not the upper and lower surface to be deposited, and foams here, and uses a product that is foamed by hardening zone similar to hard and normal temperature curing. In addition, urethanes having rigid physical properties and foamed forms have been developed in the form of continuous soft slabs, which are applicable to the automotive field.

Automotive interior processing methods have been developed to meet the above conditions, and are typically Korean Patent No. 178401 and Korean Patent No. 412228.

In the Republic of Korea Patent No. 178401, the room temperature moldable continuous bubble rigid polyurethane foam has a problem that the mixing of the raw stock solution is complicated and expensive, and when the foam is cut to a certain thickness, the skin of the skin material and the nonwoven fabric due to the generation of polyurethane powder In the case of the recent development of the automobile industry, various sizes and shapes of various types of vehicles have emerged. Thus, the foamed polyurethane in the Republic of Korea Patent No. 178401 has a variety of sizes by molding in a mold. There is a drawback to the limitation of the size to apply to the preparation of.

Polyurethanes use various types of low boiling point organic compounds. In the case of continuous bubble rigid foams, which are easy to hot-form in Korean Patent No. 412228, water and methylene chromide are used as polyurethane foaming agents. Methylene chloride is known to be harmful to the human body, and some of the low-boiling methylene chloride volatilizes when polyurethane is foamed, but it remains in the rigid foam of continuous foam, and various reinforcement materials are used by foaming foamed with methylene chloride. When the product is thermoformed and mounted on a vehicle, it gradually escapes from the bubbles of the molded foam as the temperature inside the vehicle rises, which may cause deformation (embossing) of the structure of the automobile molding, but especially methylene chloride harmful gas Get out of the bubble and give it to the driver It can be for.

In addition, in the case of Korean Patent Nos. 178401 and 412228, ester-based polyols are used. Polyester polyols have hydrophilicity, and polyether polyols have hydrophobicity and thus have low compatibility. As a result, there may occur a problem of storage stability in which separation occurs between the polyester polyol and the polyether polyol layer, and Korean Patent No. 412228 has a disadvantage of using methylene chloride, which is harmful to the human body, as a blowing agent.

Accordingly, the use of only polyether polyols is very excellent in storage stability and excellent in mechanical properties comparable to that of polyester polyols, and there is a continuing need for a method for producing an eco-friendly polyurethane foam by using only water as a blowing agent.

The problem to be solved in the present invention is to provide a rigid polyurethane foam that satisfies excellent mechanical properties by applying only a polyether polyol in order to solve the storage stability problems of the polyester polyol and polyether polyol.

Another problem to be solved by the present invention is to provide an environmentally friendly rigid polyurethane foam and a method of manufacturing the same by not using a foaming agent of a low boiling point organic compound used in polyurethane foam.

Another problem to be solved by the present invention is to provide an inexpensive foamed rigid polyurethane foam and a method of manufacturing the same using low-cost water in place of the foaming agent of the low boiling point organic compound used in the polyurethane foam.

Another problem to be solved by the present invention is to provide a method of making a polyurethane foam capable of continuous slab foaming to suit various sizes and shapes of automobiles.

In order to solve the above problems, the slab continuous rigid polyurethane foam according to the present invention is obtained by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a foaming agent and a bubble stabilizer,

Here, the polyol is
a) 10-70% by weight of a trifunctional first polyether polyol having an OH value of 10 to 100 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator;

b) 10-70% by weight of a trifunctional second polyether polyol having an OH value of 300 to 600 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator;

c) 0 to 30% by weight of a tetrafunctional polyether up to OH-V 35 to 700 as a polyether polyol obtained by addition polymerization of propylene oxide using pentaerythritol as an initiator;

d) a polyether polyol obtained by addition polymerization of propylene oxide with an initiator of sugar and glycerin, consisting of 0 to 30% by weight of polyether having 4 to 6 functional groups of OH-V 300 to 600, wherein c) and d) Cannot be zero at the same time,

The blowing agent is water,

It is characterized by consisting of 150 to 200 parts by weight of polyisocyanate to 100 parts by weight of the polyol.

In the practice of the present invention, the slab continuous rigid polyurethane foam is 0.5 to 5 parts by weight of the silicone foam stabilizer based on 100 parts by weight of the polyol; 1 to 30 parts by weight of a crosslinking agent; 1 to 10 parts by weight of water; And 0.1 to 5 parts by weight of catalyst.

In one aspect, the present invention is a resin premix for preparing a polyurethane foam comprising a polyol and a catalyst, a blowing agent and a bubble stabilizer, wherein the polyol is an OH value prepared by addition polymerization of an alkylene oxide comprising propylene oxide using glycerin as an initiator. 10 to 70% by weight of the trifunctional first polyether polyol having 10 to 100 and

10-70% by weight of a trifunctional second polyether polyol having an OH value of 300 to 600 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator.

As a polyether polyol which addition-polymerized propylene oxide using pentaerythritol as an initiator, 0-30 weight% of tetrafunctional polyethers to OH-V35-700,

A polyether polyol obtained by addition polymerization of propylene oxide using an initiator of sugar and glycerin, which is composed of 0 to 30% by weight of a polyether having 4 to 6 functional groups of OH-V 300 to 600. The foaming agent is water and a bubble stabilizer. 0.5 to 5, preferably 0.5 to 2 parts by weight; 1-30 parts by weight of crosslinking agent, preferably 10-30; 1 to 10 parts by weight, preferably 4-8 parts by weight of water, which is a blowing agent; And 0.1 to 5 parts by weight of catalyst, preferably 0.5 to 2 parts by weight.

In another aspect, the present invention provides a trifunctional polyol for preparing a slab continuous hard polyurethane foam, wherein the polyol is a trifunctional group having an OH value of 10 to 100 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator. 10-70% by weight of the first polyether polyol

10-70% by weight of a trifunctional second polyether polyol having an OH value of 300 to 600 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator.

As a polyether polyol which addition-polymerized propylene oxide using pentaerythritol as an initiator, 0-30 weight% of tetrafunctional polyethers to OH-V35-700,

A polyether polyol obtained by addition polymerization of propylene oxide using an initiator of sugar and glycerin is characterized by comprising 0 to 30% by weight of polyether having 4 to 6 functional groups up to OH-V 300 to 600.

The first polyether polyol which can be used as the polyol component of the present invention is a trifunctional hydroxyl polyether having an OH value of about 10 to 100, and an alkylene oxide containing propylene oxide is used as a trihydric alcohol (e.g. glycerin, trimethyl Trifunctional polyether obtainable by addition polymerization reaction with all propane). In the present invention, the alkylene oxide is a propylene oxide or a mixture of propylene oxide and ethylene oxide. The OH value of these polyethers is 10-100, Preferably it is 20-50, Most preferably, it is 25-30.

The second polyether polyol which can be used as the polyol component of the present invention is a trifunctional hydroxyl polyether having an OH value of about 300 to 600, and an alkylene oxide containing propylene oxide is used as a trihydric alcohol (e.g. glycerin, trimethyl Trifunctional polyether obtainable by addition polymerization reaction with all propane). In the present invention, the alkylene oxide is a propylene oxide or a mixture of propylene oxide and ethylene oxide. The OH value of these polyethers is 300-600, Preferably it is 300-400.

Tetrafunctional hydroxyl polyethers having an OH value of about 35 to 700 that can be used as the polyol component of the present invention may be used to convert ethylene oxide and / or propylene oxide to tetrahydric alcohols (e.g. ethylene diamine, toluene diamine, pentaerythritol). ) And a tetrafunctional polyether obtainable by addition polymerization reaction. These polyethers having an OH value of 35 to 700 generally correspond to about 320 to 6400 molecular weight as determined by terminal group analysis.

4- to 6-functional hydroxyl polyethers having an OH value of about 300 to 600 usable as the polyol component of the present invention can be obtained by addition polymerization of ethylene oxide and / or propylene oxide with a mixture of glycerin and sugar. 4 to 6 Functional Polyethers These polyethers have an OH value of 300 to 600, which is generally measured by terminal group analysis and corresponds to a molecular weight of about 370 to 1100.

In a preferred embodiment, the tetrafunctional and 4- to 6-functional polyol is preferably added in an amount of 20 to 30% by weight. By the use of the above-mentioned high functional polyol, the foam growth and workability of the foam according to the decrease in viscosity are improved, and the physical dimensional stability of the foam after polyurethane foaming can be improved.

In the present invention, it can be used as a crosslinking agent is a bifunctional crosslinking agent is used in about 1-30 parts by weight, more preferably 5 to 15 parts by weight based on 100 parts by weight of the total polyol, the ethylene glycol , Propylene glycol, diethylene glycol, dipropylene glycol, butanediol, trimetholol propane, 1.3 butane diol, 1,4 butane diol, glycerin, trimethol propane, monoethanol amine, diethanol amine, triethanol amine Used. In the practice of the present invention, the crosslinking agent component may be optionally added to adjust the physical properties of the polyol, preferably about 10 parts by weight or less of the total polyol component. When the amount of the crosslinking agent component is increased, the physical properties are increased by increasing the crosslinking density of the polyurethane foam, but when the content of the crosslinking agent is too large, there may be a problem in the stability of the entire polyol system.

In the present invention, water is included as a blowing agent in the polyol component in an amount of about 1 to 10 parts by weight, preferably 4-8 parts by weight, based on 100 parts by weight of the total polyol component.

In the present invention, the silicone foam stabilizer included in the polyol component is applied to be suitable for continuous foaming, and is used in an amount of about 0.5 to 5.0 parts by weight based on the total polyol component.

The catalyst used in the present invention is a tertiary amine which can be incorporated into the polyol group. Incorporable tertiary amines represent tertiary amines having at least one substituent which is an isocyanate reactive group and a secondary substituent which is a group catalyzing the reaction of an isocyanate group to the urethane group. Examples of tertiary amines that can be incorporated into polyol groups include BLOWING CATALYST, which promotes the reaction between isocyanates and water, under the trade names AIR-PRODUCT, DABCO BL-11, TOYOCAT, ET, HUNTSMAN, ZF-22, and AIR-PRODCUT, POLYCAT-. 5, HUNTSMAN's JEFFCAT PMDETA, and GELLING CATALYST which promotes the reaction of polyol and isocyanate are as follows: , DMCHA, DMEA can be used.

The polyisocyanate component comprises from about 70 to about 90 weight percent of the fraction containing two nuclei (about 12 to about 30 weight percent thereof, preferably about 15 to 24 weight percent is 2.4'-diphenyl methane diisocyanate A fraction containing three or more nuclei is MDI, which constitutes about 10-30% by weight. Preferably, fractions containing four or more nuclei are present at 3% by weight or less. Particularly preferred is MDI having the following fractions.

-2 core content: 74% by weight

content rescue 52 wt% Diphenyl Methane 4.4'-Diisocyanate 19% by weight Diphenyl Methane 2.4'-Diisocyanate 3 wt% Diphenyl Methane 2.2 "-Diisocyanate

-3 core + 4 core content: 23% by weight

-Rest (4 core or more): 3% by weight

In the present invention, the foam may be prepared by adding one or more flame retardants, plasticizers, fillers, antibacterial agents, pigments, dyes, etc. according to the required physical properties.

The foam prepared according to the present invention may be used by mixing the polyol component and the polyisocyanate component with a weight ratio of polyol to isocyanate up to 100: 150 to 200, preferably about 100: 160 to 170 in a weight ratio. It is good.

Foams prepared according to the invention are typically 20 to 30 kg / m 3 And preferably 24 to 26 kg / m 3.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

The present invention provides a rigid polyurethane foam and a method for producing the same, wherein only polyether polyol is applied to satisfy high mechanical properties while having high storage stability. In addition, the present invention provides an environment-friendly rigid polyurethane foam and automotive liner without using a blowing agent of a low boiling point organic compound.

Through the following examples, the present invention will be described in more detail. The following examples illustrate the invention in detail, but are intended to illustrate the invention and in no case to be construed as limiting the invention.

Example

Of polyol  Produce

Preparation of First Polyether Polyol: Polyol 1

As a polyether polyol to which propylene oxide is added as a glycerin initiator

Trifunctional polyether polyols having an OH value of 340 to 370 (mg / KOH)

Preparation of Second Polyether Polyols: Polyol 2

Alkylene oxide containing propylene oxide using glycerin as an initiator

Trifunctional poly group having an OH value of 26 to 30 (mg / KOH) prepared by addition polymerization

Ether polyols

Tetrafunctional Polyether Preparation: Polyol 3

Polyether to which propylene oxide was added as a pentaerythritol initiator

4-functional poly with OH values 400-430 (mg / KOH) prepared as polyols

Ether polyols

4-6 Functional Polyether Preparation: Polyol 4

Polypropylene with propylene oxide added as glycerin and sugar initiator

OH values prepared as ether polyols have 490 to 530 (mg / KOH)

4.2 Polyether Polyols of Functional Groups

Example 1

The prepared polyols 1 to 4 were mixed and foamed as in Example 1 of Table 1. The physical properties of the obtained foams are listed in Table 1.

Example 2

The prepared polyols 1 to 4 were mixed and foamed as in Example 2 of Table 1. The physical properties of the obtained foams are listed in Table 1.

Example 3

The prepared polyols 1 to 4 were mixed and foamed as in Example 3 of Table 1. The physical properties of the obtained foams are listed in Table 1.

Example 4

The prepared polyols 1 to 4 were mixed and foamed as in Example 4 of Table 1. The physical properties of the obtained foams are listed in Table 1.

Example 5

The prepared polyols 1 to 4 were mixed and foamed as in Table 1 and Example 5. The physical properties of the obtained foams are listed in Table 1.

160 parts by weight of polyphenyl polymethylene having about 12% polyisocyanate component polyisocyanate (diphenyl methane 2.4-diisocyanate isomer content is about 20%, NCO content is 31.4 to 31.8%, the viscosity at 25 ℃ About 60 ~ 100cps)

The measurement of physical properties is based on ASTM D 3574 TEST A, elongation at ASTM D 3574 TEST E, tensile strength at ASTM D 3574 TEST C, and flexural strength at ASTM D 790.

In Table 1, catalyst 1 is an example of a tertiary amine that can be incorporated into a polyol group, and the brand name BLOWING CATALYST, which promotes the reaction between isocyanate and water, uses DABCO BL-11 under the trade name of AIR-PRODUCT, and catalyst 2 is a polyol and an isocyanate. As a GELING CATALYST to promote the reaction of DABCO 33LV of AIR-PRODCUT, 1,4 butane diol is used for the crosslinking agent 1 and diethanol amine is used for the crosslinking agent 2

Comparative Example 1

The same procedure as in Example 1 was carried out except that polyol 1 was used alone in the polyol. The results are shown in Table 1.

Comparative Example 2

The same procedure as in Example 2 was carried out except that polyol 2 was used alone in the polyol. The results are shown in Table 1.

Table 1

Claims (5)

Obtained by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a blowing agent and a foam stabilizer, Here, the polyol is a) 10-70% by weight of a trifunctional first polyether polyol having an OH value of 10 to 100 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator; b) 10-70% by weight of a trifunctional second polyether polyol having an OH value of 300 to 600 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator; c) a polyether polyol obtained by addition polymerization of propylene oxide using pentaerythritol as an initiator, 0-30% by weight of a tetrafunctional polyether having an OH value of from 35 to 700; d) A polyether polyol obtained by addition polymerization of propylene oxide using an initiator of sugar and glycerin, and has an OH value of 0 to 30% by weight of polyether having 4 to 6 functional groups of 300 to 600.  Here, c) and d) may not be 0 at the same time, The blowing agent is water, Slab continuous hard polyurethane foam, characterized in that consisting of 150 to 200 parts by weight of polyisocyanate to 100 parts by weight of the polyol. According to claim 1, The slab continuous rigid polyurethane foam is 0.5 to 5 parts by weight of the silicone foam stabilizer with respect to 100 parts by weight of the polyol; 1 to 30 parts by weight of a crosslinking agent; 1 to 10 parts by weight of water; And 0.1 to 5 parts by weight of catalyst. Slavi continuous rigid polyurethane foam, characterized in that comprises. The slab continuous hard urethane foam according to claim 1, wherein the slab continuous hard urethane foam has a molding density of 24 to 26 kg / m 3. In the polyol for producing rigid urethane foam, 10-70% by weight of a trifunctional first polyether polyol having an OH value of 10 to 100 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator; 10-70% by weight of a trifunctional second polyether polyol having an OH value of 300 to 600 prepared by addition polymerization of an alkylene oxide containing propylene oxide using glycerin as an initiator. A polyether polyol obtained by addition polymerization of propylene oxide using pentaerythritol as an initiator, 0-30% by weight of a tetrafunctional polyether having an OH value of 35 to 700, A polyether polyol obtained by addition polymerization of propylene oxide using an initiator of sugar and glycerin, wherein the polyol composition comprises 0 to 30% by weight of polyether having 4 to 6 functional groups with an OH value of 300 to 600. 5. The polyol composition according to claim 4, wherein the OH value of the first polyether polyol is 20-30 and the OH value of the second polyether polyol is 300-400.