JPS6186205A - Manufacture of lignocellulose group isocyanate molded composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is applicable to the compression molding of lignocellulosic materials into composites, sheets, etc., particularly the production of particle boards using polyisocyanate binders, and the prevention of mold release and warpage from the mold surface. The present invention relates to the use of a functional polysiloxane-monocarboxylic acid or metal salt copolymer thereof as a mold release agent that can easily provide mold release.

lignocellulosic and lignocellulose-containing fibers,
It is well known that particles or layers can be formed into bonded products.
I'm here. Organic di- and polyisocyanates as useful binders for lignocellulosic materials have been known for some time and provide greater stability and mechanical strength to particleboard raw materials (e.g., U.S. Pat. No. 3,428
, No. 592, No. 3,440,189, No. 3,55
No. 7,263, No. 3,636,199, No. 3.8
No. 70,665, No. 3,191,017 and No. 3
, 930, 110). It is also known in the art that incyanate binders are mixed with wood particles that are utilized as substrates for particleboards. The mixture of wood chips or particles and incyanate binder is then matt IIc! FC shape tongue and molded into desired size or shape by pressure and temperature. Water emulsion polyisocyanate binder systems are also known for use with lignocellulosic particles to make particleboard. The main drawback of the use of incyanates in the production of particleboard is due to their excellent adhesive properties. Therefore, isocyanate systems, whether water emulsions or pure polyisocyanate binders, adhere tenaciously to the metal caul plates used to support the wood particles during transport and pressing or molding processes. This inability to easily separate the molded particle board from the caul plate or metal plate surface also creates difficulties in cleaning and automatic handling of the caul plate. To avoid this sticking problem, for example, a US patent! No. 4,110,397, an external mold release agent was developed and applied to a face plate or hot plate or mat surface. Other conventional mold releases such as oils, waxes, polishes, silicones and polytetrafluoroethylene are unsatisfactory, as are specialty urethane mold releases, including those used in structural foam applications. Met. Other ways to overcome the sticking problem are described, for example, in U.S. Pat. No. 3,390,110;
No. 19 and M3.191,017, a single wood material (veneer) was laminated to the incyanate-bonded lignocellulosic particles using fctlj release paper. These methods have the disadvantage of increasing product costs or underutilizing the advantages of isocyanate binders. Many of the mold release agents developed to date must be applied in large amounts during each composite tear cycle in order to be effective.

In the present invention, when molding a mixture of lignocellulose particles and a polyisocyanate binder between the mold surfaces, the mold surface is coated with a functional polysiloxane and a monocarboxylic acid or warped metal salt. The copolymer is provided as a mold release agent, which can also be mixed with an organopolysiloxane liquid as a diluent, providing a method for making lignocellulosic bonded articles or plates.

One object of the present invention is to provide a new composition that serves as a mold release agent and is utilized for repeated demolding of molded articles.

The purpose of the invention is to provide a mold release agent that is easily applied and adhered to the mold surface.

Yet another object is to provide mold release agents that require only small amounts of application.

The above ACL and other objects of the invention will be apparent from the specification and claims of the invention.

The present invention will be explained in detail below.

The present invention uses heat and pressure to form a mold release agent film by dipping, spraying or rubbing a copolymer of a functional polysiloxane and a monocarboxylic acid or a metal salt thereof with an organic polyisocyanate used as a binder. A process for producing lignocellulosic composite molded articles, in particular particleboard, by adhesively bonding wood chips or other lignocellulosic or organic materials by providing a formula (where n n is an integer from 5 to 30). and mke1~CH
.

A functional polysiloxane of the formula CH3 -Coo), -COW or -OR
-(CH2)y -C00z (wherein, 3'l'fj
There is an integer T of ~24, and iZ is H, Na1Li, C
The copolymer mold release agent of the present invention is produced by reacting a monocarboxylic acid represented by (a, Ba, Cd, Mg, K or Fe) or a metal salt of the monocarboxylic acid. . For essentially permanent mold release or longer manufacturing use cycles, the thin film coated mold surfaces are heated to 75-200°C for 1-5 minutes prior to use.
It can be heated to

Molded lignocellulosic bonded articles, such as particle hoard or flakeboard, are generally prepared by spraying a polyisocyanate binder onto the particles while they are mixed or stirred in suitable conventional equipment such as a blender. Manufactured by ζ. Advantageously, the polyisocyanate binder usage level is about 1.5 to 12% by weight of the oven-dried (0% water content) lignocellulosic material.
Deuterium chloride, preferably 2.5 to 6.5% by weight. Other materials, such as flame retardants, may also be added to the particles or sprayed with the binder during the blending or mixing process. After forming a homogeneous mixture, the applied lignocellulosic particles may be added to the particles in the desired proportions. , formed into a loose mat or felt on a polished aluminum or steel caul plate 1, and this caul plate serves to carry this so-called "cake" into a heated press, in which the wood particles are consolidated. , to obtain a board of desired thickness. The temperature of the press is generally 1
The temperature is 40-220℃ and the pressure is about 7.03-42.2
kg/i (100-600 psi). Pull time, temperature and pressure will vary widely depending on the thickness of the plank being produced, the desired density of the plank, the size of the lignocellulosic particles used and other factors well known in the art. .

The isocyanate binder may generally be an organic polyisocyanate used alone, or may be mixed with a middle type binder, such as a synthetic resin adhesive, or mixed with a diluent such as propylene carbonate. You may. Isocyanates are liquid and can be applied as solutions in inert solvents or in the form of aqueous emulsions.

The polyisocyanate component used in the binder system in this invention may be any organic polyisocyanate, including aliphatic, fatty, and Includes cyclic and aromatic polyisocyanates. Such polyisocyanates include diisocyanates! Contains isocyanates of higher functionality. Mixtures of polyisocyanates have been created, for example by phosgenation of aniline-formaldehyde condensates, as also described in U.S. Pat. No. 3,962,302 and U.S. Pat. Mixtures of polyinsyanates of high functionality can be used. Polyisocyanates are prepared by converting excess polyisocyanate under standard known conditions to polyols such as polyethylene glycol, polypropylene glycol, triethylene glycol, etc., as well as glycols and polyglycols (polyesters) partially esterified with carbonic acid. (including polyols and polyether polyols), in a ratio of about 20=1 to 2=1 polyisocyanate to polyol groups. Examples of organic polyisocyanates that can be used include toluene-2,4- and 2,6-diisocyanate or
mixture of diphenylmethane diisocyanate, m-
and p-phenylene diisocyanate or mixtures thereof, m- and p-diphenylene diisocyanate, polymethylene polyphenylisocyanate, naphthalene-1,
5-diisocyanate, chlorphenylene diisocyanate, α,α-xylene diisocyanate, triphenylmethane triisocyanate, hexamethylene diisocyanate, 3,3'-citrilene-4,4-diisocyanate, butylene 1,4-diisocyanate, octylene-1 .8-diisocyanate, 1,4-11,3- and 01.2-cyclohexylene diisocyanate and generally U.S. Pat. No. 3,577,358; n I
2. n O8 and 3. No. 97,191 contains F-celled polyisocyanates.

Preferred polyisocyanates are diphenylmethane diisocyanate 2.4' and 4.4' isomers (including the 2,2' isomer) and higher functionality polyisocyanates and polymethylene polyphenylisocyanate compositions (approximately 20 to 85 mm). may contain diisocyanate isomers). Typical 1 of the preferred polyisocyanates! ，
(7) n r Rubinate − M J (
Rubicon Chemical Inc. ) is commercially available. Generally, organic polyisocyanates are about 100 to 10. It has a molecular weight in the range of 0 0 0. Aqueous organic polyisocyanate 1'f? The silocyanate-terminated prepolymer emulsion is prepared by using any technique known in the art for the preparation of aqueous emulsions or dispersions prior to use of the composition as a binder. Generally, the polyisocyanate is dispersed in water in the presence of an emulsifier or surfactant (which may be any emulsifier also known in the art, including anionic and nonionic agents).

Preparation of aqueous emulsions is described in U.S. Pat. No. 3,996.
1 5 4, 4 Pj 4.1 4 3,0 1 4 and 4,257,995 for producing molded assemblies using polyisocyanate binders. Lignocellulosic materials used include wood chips, wood fibers, planer shavings, sawdust, wood wool, cork, bark, and products obtained from the ice processing industry. Other natural products that are lignocellulosic, such as wheat straw,
Fibers, particles, etc. from flax residue, grass, nut husks, or the husks of grains such as rice and oats can also be used. Furthermore, lignocellulosic materials include not only granular rubber and plastic materials, but also inorganic flakes or fibers? 1 material phase,
For example, it can be mixed with glass fibers or wool, mica and asbestos. The lignocellulose can contain a water content of less than about 25% by weight, but preferably less than 4% to 1% by weight.
contains water.

The mold release agent of the present invention comprising a copolymer of a functional polysiloxane and a monocarboxylic acid or a gold salt thereof contains about 50 to
At a temperature of 1511℃, 90~1]0℃,
4-modulo formula (where n is an integer from 5 to 30, m is an integer from 1 to 20, and X is 1 CHzOH 1-C) [)H
A silanol-terminated functional polysilane of the formula Cl-11-(C)J2)y-COO 'z
(wherein y is a number from 5 to 24 and 2 is prepared by selection from hydrogen, Na%Li, Ca.Ba%Cd1M9, K or Fe). For example, 12-hydroxystearic acid may be used.Incidentally, an inert solvent such as toluene, xylene, benzene, heptane, hexane, etc.
It can be carried out in the presence of aromatic or aliphatic hydrocarbons such as those of San et al. A solution with a solids content of 5 to 50% can be prepared by a condensation method, but is preferably prepared and applied as a solution with a solids content of 0 to 20%.

Typical monocarboxylic acids or metal salts that can be used to prepare the copolymers include, for example, capric acid, lauric acid,
These include palmitic acid, stearic acid, oleic acid, lyluic acid, etc., as well as potassium oleate, calcium stearate, iron stearate, sodium palmitate, cadmium stearate, and magnesium dodecanoate.

As shown above, the organopolysiloxane liquid is copolymerized as a diluent with functional polysiloxane-monocarbon 6
It is used as a monocarboxylic acid or monocarboxylate mold release agent in a weight range of 10 to 20% by weight. Organopolysiloxane fluids suitable for use in the present invention are generally alkyl terminated polysiloxane fluids having from 1 to 18 silicon-bonded carbon atoms. Examples of suitable organopolysiloxane liquids include methyl, ethyl, propyl, butyl, hexyl,
Alkyl groups such as octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl.

Generally, it is preferred that the organopolysiloxane contain no terminal hydroxyl groups. However, the small number of terminal hydrosil groups does not substantially affect the mold release composition. The organopolysiloxane can have a small proportion of molecules with only one hydroxyl group, or it can have a small proportion of molecules with more than two hydroxyl groups. However, as mentioned above, it is preferred that the organopolysiloxane has substantially no hydroxyl groups. Generally, the boryleloxane liquid is about 3.
It must have a molecular weight of 000 to 90,000. This molecule 11 corresponds to about 50-5,000 centipoise, preferably about 1110-5,000 centipoise. Optimum results are obtained from here on in the lower part of the range, e.g. Can be combined.

The organopolysiloxane liquid used according to the invention has the formula:
It is preferably represented by "yhso", which indicates an alkyl group having ~4 carbon atoms and has a value of about 150,000 from yhso.

The novel mold release agent of the present invention can be prepared by mixing the copolymer ν1 alone or the copolymer with an organopolysiloxane liquid, preferably sufficiently volatile to evaporate during the application process. Use in liquid organic solvents. Preferred solvents include toluene, xylene, benzene, naphtha type solvents, higher C4-C2 alcohols such as isobutanol and hydrocarbon solvents such as tsO-chloroethylene.

The copolymerized mold release agent of the present invention can be applied to the mold surface as a concentrated or diluted solution or as a dispersion.

The mold release agent composition is preferably dissolved in a volatile organic solvent such as a mixture of badruene and isobutanol and applied to the mold surface by misting, rubbing or brushing 11R. This is best obtained by rubbing the mold surface with a cotton swab saturated with a mold release composition solution.

However, in actual cases, the composition may be sprayed onto the mold surface to form Wj Ill thereon.

Once the mold release composition is applied to the mold surface,
This can be used immediately. However, it is advisable to allow the coating to dry, especially if a coated mold has been used. More preferably, as pointed out above, the coated mold surface should be Heating for 1-5 minutes at 0.degree. C. fills all pores and openings and lends itself to essentially permanent demolding or longer manufacturing use cycles.

Examples are listed below to illustrate the present invention in accordance with the principles of the present invention, including those of the nature of Comparative Example 1.
They are not intended to limit the invention in any way except as indicated by the claims.

EXAMPLE Six dried 5809 wood chips were placed in an open tumbler mixer. During inversion, diphenylmethane diisocyanate-polymethylene polyphenylene isocyanate (PMDI) mixture 1 with a diphenylmethane diisocyanate content of 46.5% as binder
6 g was sprayed uniformly onto the wood chips by an air compression system. 2 new aluminum caul plates 30.48α (12
”)×30.48m(12”)×O,476m(3
/1B">k, 10 parts by weight of silano u, (-CH20H)-terminated polydimethylsiloxane and 12-hydro-distearic acid ""
Atypical combination and 90! Wipe with a cloth soaked with a mixture of 1 part toluene. The silanol (-C)i, U)I) of this copolymer (hxiit)-terminated siloxane and 1 part by weight of 12-hydro-distearic acid were added to a 250-ml reaction flask in 50'EI(4i)'lx of toluene. It was manufactured by first preparing it so that it was. The reaction was carried out at 95°C for 4 hours under nitrogen and steady stirring. The reaction was cooled and diluted with toluene to a 0% solids solution.

Next, the wood chips coated with polyisocyanate are
26.7 cm (10,5 inches) square 30.5 cy
Thick mats were formed by preforming and prepressing in a box supported by one of the ++ (12 inch) high release agent applicator plates. The box was then removed and a second application plate was placed on the mat. The whole assembly is 190
℃ and pressed to a thickness of 13 cm, held for 4 minutes and released the pressure. Easily separates lignocellulosic (wood chipboard) composite products from the backing board. Using the same caul plate that was applied from the beginning, the above-described plate manufacturing method was repeated six more times, and the composite product was easily released from the mold.

Example 2 An aluminum patch wiped with a silanol-terminated polydimethylsiloxane-12-hydroxystearic acid copolymer mold release agent having a molecular weight of 28>000 was heated at 176°C for 3 minutes before use.
The method of Example 1 was repeated except that the mixture was heated at . 190℃
Seven repeat cycles of plank production and demolding were recorded.

Examples 3-8 Silanol-terminated polydimethylsiloxane (928.
000) and various copolymers with monocarphonic acids or metal salts thereof, 1 part by weight of silanol and 13 parts of acid or gold B4* were mixed in a reaction flask containing 250+/50% of
Manufactured by reaction with 0 parts by weight toluene. The reaction was carried out for 4 hours at 95° C. under stirring under nitrogen, cooled and diluted with toluene to bring the 10% solids solution to m
Ta. Particle board was produced by repeating the method of Example 1 for 1 m using a mold release agent and providing a mold release period as shown below.

Implementation 1: Copolymer mold release agent: Add siloxane and calcium stearate to 190°C.
54 Silanol (-CH20H)-terminated polydimethylsiloxane and iron stearate 65 Carbinol (-
GO) l) Terminated polydimethylsiloxane and potassium oleate 66 sulfoxy (-C
OOH) terminal polydimethylsiloxane and 12-hydroxystearic acid
77 Silanol (-C1-120) 1) Terminal polydimethylsiloxane and cafiric (decanoic) acid
68 silanol (-CM, 0)t) terminal polydimethylsiloxane and valmitic (hexadecanoic) acid
7 Example 9 The procedure of Example 2 was repeated using 85% of the copolymer of Example 1 mixed with 15% of the polysilicon liquid and diluted with 10% solids solution in toluene. Six repeat cycles of particleboard production and demolding at 190°C were arranged.

Example: 0 50:501'-109 in isobutanol mixture
The method of Example 2 was repeated using an 80:20 mixture of the copolymer of Example 3 and polydimethylsiloxane diluted to 1.6%.

Example 11 (Control) The method of Example 1 was repeated except that no mold release agent was applied to the caul plate. The pressed lignocellulosic composite article could not be demolded even after cooling. Example 12 (Control) The caul plate in the production of three composite articles was prepared using zinc stearate, aluminum stearate and stearin in isobutanol. Examples 1 and 2 were repeated except each was wiped with a 15% solution of lithium oxide.

Two demolding cycles of only one demolding cycle each were recorded at high temperature (190° C.).

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Claims (23)

[Claims] (1) In forming a molded article by contacting lignocellulosic particles with an organic polyisocyanate binder composition and then applying heat and pressure to the treated particles,
In order to facilitate the release of lignocellulosic molded products, a thin coating film of a copolymer reaction product of a functional polysiloxane and a monocarboxylic acid or its metal salt is provided on the mold surface, and the functional polysiloxane has the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is an integer from 5 to 30, m is an integer from 1 to 20, and X is -CH_2OH, ▲There are mathematical formulas, chemical formulas, tables, etc.) ), and the monocarboxylic acid or metal salt thereof has the formula CH_3-(CH_2)y-COOz, where y is 5 to
is an integer of 24, and z is hydrogen, Na, Li, Ca
, Ba, Cd, Mg, K or Fe). (2) The method according to claim (1), wherein the lignocellulosic composite molded product is a particle board. (3) The lignocellulosic composite material is approximately 4.
Temperature of 0~220℃ and about 7.03~42.2kg/c
The method according to claim 1, wherein the method is compressed for 1 to 10 minutes under a pressure of 100 to 600 psi. (4) Claim No. (3) that the time is 3 to 5 minutes.
The method described in section. (5) The method according to claim 1, wherein the surface of the coated mold is heated at a temperature of about 75 to 200° C. for about 1 to 5 minutes before producing the lignocellulosic composite molded article. (6) The method according to claim (1), wherein the organic polyisocyanate binder is diphenylmethane diisocyanate. 7. The method of claim 1, wherein the organic polyisocyanate binder is a polymethylene polyphenyl polyisocyanate containing about 20-85% by weight of Cyphenylmethane diisocyanate. (8) The method according to claim (1), wherein the functional polysiloxane has -CH_2OH as a terminal group. (9) The method according to claim (1), in which the functional polysiloxane has ▲a mathematical formula, a chemical formula, a table, etc.▼ as a terminal group. (10) The method according to claim (1), wherein the functional polysiloxane is terminated with -COOH. (11) The method according to claim (1), wherein the monocarboxylic acid of the copolymer is 12-hydroxystearic acid. (12) The method according to claim (1), wherein the monocarboxylic acid of the copolymer is palmitic acid. (13) The method according to claim (1), wherein the monocarboxylic acid salt is calcium stearate. (14) The method according to claim (1), wherein the monocarboxylic acid salt is iron stearate. (15) The method according to claim (1), wherein the monocarboxylic acid salt is potassium oleate. (16) The method according to claim (1), wherein the monocarboxylic acid of the copolymer is stearic acid. (17) The method according to claim (1), wherein the functional polysiloxane-monocarboxylic acid or metal salt copolymer is applied as a mixture together with a solvent. (18) The solvent is toluene, claim (17)
) Method described in section. (19) The method according to claim (17), wherein the solvent is isobutanol. (20) The method according to claim (1), wherein 0 to 25% by weight of the organopolysiloxane liquid is added as a diluent to the copolymer-organopolysiloxane liquid mixture. (21) The method according to claim (20), wherein the organopolysiloxane liquid is 10 to 20% by weight. (22) Facilitating the release of lignocellulosic molded articles for forming planks by contacting wood particles with an organopolyisocyanate binder composition and then applying heat and pressure to the treated particles. Therefore, a thin coating film of a copolymerization reaction product of a functional polysiloxane and a monocarboxylic acid or its metal salt is provided on the mold surface, and the functional polysiloxane has the formula ▲ mathematical formula, chemical formula, table, etc. ▼ (formula In, n is an integer from 5 to 30, m is an integer from 1 to 20, and -COOH or -OH), and the monocarboxylic acid or its metal salt has the formula CH_3-(
CH_2)y-COOz (where y is an integer from 5 to 24, and z is hydrogen, Na, Li, Ca, Ba, Cd
, Mg, K or Fe). (23) A composition plate product comprising a compression-molded lignocellulosic molded article produced by the method described in claim (1).