CN1150443A

CN1150443A - Resilient inlaid products and method for making such products

Info

Publication number: CN1150443A
Application number: CN 95193326
Authority: CN
Inventors: A·N·皮亚森; D·R·辛尼尔; G·J·帕普
Original assignee: Congoleum Corp
Current assignee: Congoleum Corp
Priority date: 1994-04-05
Filing date: 1995-04-05
Publication date: 1997-05-21
Also published as: JPH10511301A; EP0754203A1; AU2278095A; EP0754203A4; WO1995027007A1; CA2186393A1; MX9604647A

Abstract

Disclosed are products and processes which utilize a reactive matrix (70) containing decorative elements to form the wear layer of a resilient, inlaid flooring product. The inlaid layer of the preferred floor covering products comprises an interpenetrating polymer network and a plurality of decorative elements at least partially embedded in the interpenetrating polymer network. The method aspects of the invention include consolidating the matrix (70) by exposure to elevated pressure and initiating polymerization of the reactive components in the matrix during the consolidation step.

Description

Elasticity embossing product and manufacture method thereof

Related application

The application be submitted on May 25th, 1993, the part continuation application of No. the 08/66th, 568, existing pending application sequence.

Invention field

The present invention relates to embossing veneer product and manufacture method thereof.Specifically, the present invention relates to comprise the veneer of ground, wall and top ceiling, and be used for desk, desk and counter surface as flexible overlays, so the modified form embossing sheet material of automotive interior trim etc.

Background of invention

Elasticity embossing sheet material has purposes widely as surface coating material, and is taken as the part of attrition resistant surface or wearing face usually, is used as the veneer of ground, wall and top ceiling.Here said embossing one speech refers to the ornamental flaked product of a class, it is characterized in that a wearing layer, and described wearing layer still can keep certain constant ornamental composition of outward appearance after comprising experience wear.

Traditionally, elasticity embossing veneer comprises that contains a resin material, for example the wearing face of pellets such as resin slicer, fragment, particle or bead.According to a kind of known manufacturing process of this kind product, add that at the base material of veneer or above the backing part granulated material of different colours and/or shape has just formed ornamental intarsia pattern or pattern.Common decorative pattern or the pattern that adopts one group of stencil (stencil) that particle is arranged to require, so this paper claims this stencil type (stencil built-up) the embossing product that is configured to sometimes.Subsequently, allow the resin particle in this product under heat and pressure, press solidly, the formation wearing layer, and this decorative effect is applied in the whole thickness of this layer basically.

According to some newer manufacturing technology, the embossing feature is to realize by form the matrix that comprises tackiness agent and resin granulated material at substrate surface.In this structure, this matrix is a stratiform through shaping under suitable pressure and temperature condition, and wherein the decorative effect that is formed by resin particle is through whole layer.This paper is referred to as matrix configuration to this embossing structure sometimes, and this structure, for example can be seen in No. the 4th, 212,691, people's such as Potosky United States Patent (USP).

Though known have various elasticity embossing overlay type, one of modal type will be calculated the matrix embossing class that comprises the thermoplasticity granulated material that bonds with thermoplastic adhesive composition.General up to now way is to utilize polyvinyl chloride (PVC) plastisol composition as thermoplastic adhesive composition in this class embossing floor surfacing.

Those skilled in the art understands that embossing type floor (veneer) product is different from non-embossing product in many importances.For example, owing to contain ornamental granulated material in the wearing layer of embossing flooring products, making it can produce the other types flooring products is not impossible be exactly the aesthetic effect that is difficult to produce.It is widely acknowledged that the embossing goods can accomplish to possess 3-D effect and the various texture appearance that makes us very yearning for.And human consumer and other users usually feel, compare with non-embossing material, and the embossing veneer has extraordinary weather resistance and high-quality.Just because of above-mentioned and other performance, elasticity embossing flooring products gains great popularity in flooring products industry at large.

Though the elasticity embossing flooring products of traditional form has obtained such success, the applicant recognizes that this traditional embossing goods still exist some parts that are left to be desired.For example, but this people's of most of embossing goods outward appearance is mainly derived from the characteristic of used decorative particles, and this particle, could be selected after the particular design purpose that is fit to the floor producer often only through extensive studies and analysis.Yet the manufacturing technology that generally adopts causes sometimes at present, produces its aesthstic performance considerable fault at least easily and closes the product of design requirements.Specifically, the typical method of preparation matrix type embossing veneer comprises, ornamental section or fragment are added in the base material or the thermoplasticity plastipaste adhesive coating on the substrate surface such as felt.Then, go up plain roll to containing heating of particulate thermoplasticity plastipaste and/or pressurization, make it to press solidly and plastify by heating drum and/or pressurization.For example, can be referring to No. the 4th, 212,691, people's such as Potosky United States Patent (USP).

Yet the applicant recognizes, owing to press solidly and/or the plastifying result, occurs undesirable decoration particle " striped (streaking) " phenomenon sometimes.Here said fringe phenomena refers to decorative particles, and especially ornamental resin particle tends to along passing through around drum when dalle, and/or sheet material travel direction distortion or extend this phenomenon when going up plain roll and pass through pressurization.Therefore just damaged and wished being imbued with aesthetic feeling and/or having the outward appearance of texture of the embossing veneer that obtains, perhaps do not reached and beautify effect.

The applicant also recognizes, the feel of the embossing flooring products of some prior art, or the sensation of giving the people need to improve.Here said " feel " refers to the appropriate balance of embossing sheet material between elongation and tensile strength.The defective that the prior art embossing goods of producing with the stencil manufacturing process often exist is, they make us sending out offensively deadlock, and its elongation index is low excessively in other words.This shortcoming has also increased the difficulty when this based article is installed, and especially is made into wide cut when this based article, and in the time of for example more than 6 feet, situation is even more serious.Correspondingly, this characteristic makes these goods so not satisfactory, thereby commercial also so not successful.

On the other hand, the embossing product of producing according to the binder matrix technology usually is considered to too soft, and its elongation numerical value is too big in other words.These characteristics are not satisfied, because the human consumer usually feels that the softish flooring products is of poor quality.

In addition, the applicant thinks, some article of commerce of producing according to the binder matrix technology falls into aspect (indentation resistance) relatively poor in resistance to compression, and particularly the embossing goods made according to the stencil forming technique of beguine are poor.Here said " resistance to compression fall into " speech refers to repeatedly and/or under the condition of long-time pressurized, and the ability that falls into is pressed in the surface coating material opposing.For example, stand heavy impact and/or during because of the floor of the so-called high circulating area of the concentrated load that causes such as objects such as tables and chairs when the embossing veneer is used as, its resistance to compression falls into and just seems and be even more important.

Summary of the invention

The applicant has found the embossing veneer product and the production method thereof of improvement.Product of the present invention and method have overcome that the applicant recognizes formerly the many shortcomings that exist in product and the method, comprising those shortcomings above-mentioned.Specifically, the applicant finds, utilize a kind of reactive matrix that contains ornamental composition to form the product and the method for wearing layer, the elasticity embossing flooring products of producing possesses improved feel, especially compare with the stencil shaping prod, and improved resistance to compression is sunken, especially with according to the embossing product of traditional binder matrix technology compares.Preferably slab products of the present invention is a kind of like this elasticity embossing flooring products, and embossing layer wherein comprises a kind of interpenetrating polymer networks and various decoration primitive (decorative element) that is embedded at least in part in the said interpenetrating polymer networks.

Method of the present invention preferably includes and allows this matrix stand high pressure to press solidly making it, and presses solidly the polymerization between the minimum initiation reaction component in the process in matrix, is processed into the embossing wearing layer thereby will contain the reactive matrix of particulate.The applicant finds that such procedure of processing can significantly be eliminated the stripes problem that has method to bring earlier.

Product of the present invention and method also have other advantageous characteristic feature, will become very clear after the detailed Description Of The Invention of these features below reading.

The accompanying drawing summary

Each width of cloth among Figure 1A, 1B, 1C, 1D and the 1E all is the schematic diagram about one embodiment of the invention, has showed preferred and the typical method and the equipment of this scheme.

The detailed description of preferred embodiment

I, product

Preferred veneer product of the present invention comprises the embossing wearing layer of a matrix configuration. Importantly, So a kind of wearing layer of preferred product comprises many being embedded at least in part and contains the interpenetrating polymer net Decoration primitive in the composition of network.

A, decoration primitive

Here said decoration primitive one speech refers to a kind of composition of wearing layer, and it is loaded with or shows discontinuous decorative effect.Usually preferably, this decoration primitive comprises decorative particles, and more preferably comprises ornamental resin particle.

This decorative particles can comprise section, fragment or the particle with the resinous polymer preparation of compositions, said composition contains synthetic resins, softening agent, filler, light and thermally stable agent, dyestuff, tinting material and pigment, and any other composition of wishing traditionally or requiring.For some preferred a kind of ornamental resin particle of embodiment institute is that class well known in the art is done blend polyvinyl chloride resin particle.

Decorate the embodiment that primitive comprises resin chips according to it, the various selected components of fragment prescription are by suitable means, for example be configured as the sheet material of required thickness by polishing machine cylinder or employing pressing method, the sheet material that obtains so then is transformed into the geometrical shape of requirement again, for example square, the revolution bodily form (spheroidol), trilateral, circle, annular, other Polygonss etc., perhaps irregular size and dimension, one of the perhaps above-mentioned or whole shape that mixes.If wish to have multiple color and tone, just prepare multiple independent sheet material like this, each has own independent tinting material, dyestuff or pigment, then these sheet materials are cut into the size of requirement and shape separately and subsequently with they ratio blending, to obtain pleochroic effect by hope or requirement.Can also use the sheet material of different thickness.The particulate detail of Shi Yonging is disclosed in people's such as Potosky No. the 4th, 212,691, the United States Patent (USP) in detail in these embodiments, and this article is received people this paper as a reference.

Be used to make the main decorative pattern or the pattern as requested of thickness of the various sheet materials of ornamental section or fragment, and the thickness of preparing at last these sections or fragment are embedded reactive adhesive layer wherein decides.Under normal circumstances, about 3 times of the about 1-of the sheet thickness of employing, preferably about 2-about 3 times to not dried, be clamminess, the thickness of the reactive plastipaste material of gelation not.Such thickness range is generally about 5 mils-Yue 60 mils, is preferably about 45 mils-Yue 55 mils.Nature can get up to use all thickness difference, the ornamental section with certain geometrical shape or fragment blending.

The thickness of ornamental section or debris layer just be taped against not dried, be clamminess, amplitude of fluctuation is very big on the reactive plastipaste surface of not gelation the time, but be generally 3 mils-Yue 30 mils, perhaps thicker, decide on hope or environment and condition.

Ornamental section or fragment do not require it all is plasticity.Be similar to and toply saidly like that adopt the tinsel that has applied painted vinyl coating in advance, for example the fritter of aluminium foil, section or fragment can obtain special ideal effect.As top said, these materials are made sheet material, change into various geometrical bodies then as required.Tinsel can be as thin as about 2 mils as thin as a wafer, even is as thin as 0.6 mil.Tinsel even can be embossing is so that give its extra gloss.The longest or the overall dimension of this ornamental section or fragment is about 50 mils or 100 mils, under some situation even up to 500 mils.

B, interpenetrating polymer networks

Interpenetrating polymer networks (IPN) is a class specific polymers blend, and wherein two or more polymkeric substance coexists as in the structure of abundant networking.Here said interpenetrating polymer networks refers to true IPN, apparent IPN, half IPN and their combination or mishmash.

True IPN refers to a kind of like this polymer network, and the polymkeric substance itself that wherein is in the system that is made of two or more polymkeric substance is crosslinked, yet not crosslinked mutually.In such network, some polymeric systems of boundary distinctness constitute the network that runs through each other.Half IPN refers to a kind of like this polymer network, and wherein a kind of polymeric system exists with the non-crosslinked state, and second kind of polymeric system be self-crosslinking then.Apparent IPN refers to the continuous IPN phase of a plurality of coexistences, and wherein not having a kind of polymkeric substance is chemically crosslinked, yet they are still stablized against the crosslinked polymer point of physics.

Though according to expectation, IPN of the present invention can be made of various types of polymer materialss, generally preferably, this IPN comprises at least a first thermoplastic polymer and at least a thermosetting polymer of IPN with it.As everyone knows, thermoplastic polymer is not a cross-linked polymer usually, and that thermosetting polymer is generally is partial cross-linked at least.Therefore, in such preferred embodiment, IPN comprises half IPN and/or apparent IPN.

Though, can use for reference various IPN forming techniques according to expectation, make it to be applicable to product of the present invention, preferred technology be with partly described in detail in conjunction with method of the present invention below that is a kind of.

C, thermoplastic polymer

Being used for the preferred thermoplastic polymkeric substance of product embossing layer IPN part of the present invention, is Vinylite, is more preferably polyvinyl chloride (PVC) RESINS.Though preferred thermoplastic comprises the PVC homopolymer, but there are many other Vinylites also can use, for example vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, and the multipolymer of vinylchlorid and other vinyl ester, for example vinyl ester of vinyl butyrate, propionate and alkyl replacement.

Equally preferably, this vinyl polymer comprises that class plasticising vinyl polymer that floor industry is known.Can use traditional softening agent for reaching this purpose, but usually preferably avoid using co-plasticizer.Suitable manufacturing methods comprises Uniflex DBS, dioctyl sebacate, butyl benzyl sebacate, sebacic acid dibenzyl ester, Octyl adipate, didecyl adipate, dibutyl phthalate, dioctyl phthalate (DOP), dioctyl phthalate, phthalic acid dibutoxy ethyl ester, Unimoll BB, phthalic acid dibenzyl ester, phthalic acid two (2-ethylhexyl) ester, alkylaryl modification phthalic ester, alkylaryl hydrocarbons, Tritolyl Phosphate, ODPP, dibenzoic acid dipropylene glycol ester, and diprotic acid glycol ester.

D, thermosetting polymer

Can be used for preparation according to preferred IPN of the present invention in respect of many thermosetting polymers in advance.But the applicant finds that acrylic polymers can provide well-content result.Preferably, acrylic polymers of the present invention is by comprising reactive acrylate's compound, more preferably is made up of it basically, and most preferredly is made up of reactive multi-functional acrylate's compounds--composition constitutes.Reactive acrylate example and preferred is reactive acrylate monomer and oligopolymer.Here said " acrylate monomer " and " origoester acrylate ", the general reference to contain vinylformic acid or ester moiety (H ₂C=CHCO ₂R, wherein R for example is a hydrogen or alkyl) for feature, belong to low-molecular-weight compound basically.

Especially suitable acrylate monomer is multi-functional acrylate's monomer, promptly replaces the monomer of going up two or more vinylformic acid or ester group.This preferred compound refers to that in this article functionality is about the acrylate monomer more than 2 or 2.

According to some preferred aspect of the present invention, this acrylate monomer comprises the reaction product of alcohol and vinylformic acid reagent." vinylformic acid reagent " and a speech refer to vinylformic acid and/or can with the vinylformic acid analogue of alcohol reaction.By inference, alcohol can comprise one or more reactions pure and one or more vinylformic acid reagent with the reaction of vinylformic acid reagent.Here said alcohol, refer to any contain one or more can with the substituent organic compound of the hydroxyl of vinylformic acid reagent react.Therefore, generally speaking, can comprise monohydroxy-alcohol, dibasic alcohol, trivalent alcohol and polyvalent alcohol with the alcohol of vinylformic acid reagent react.

According to some preferred embodiment of the present invention, monomer comprises the reaction product of dibasic alcohol and vinylformic acid reagent.Preferred glycol comprises ethylene glycol, propylene glycol, 1,6-hexylene glycol and neopentyl glycol.One is particularly suitable for example plastisol composition 28, dibasic alcohol and vinylformic acid reagent react product is dimethacrylate 1, the own diester of 6-.This material is a commercially available product, is produced by Sartomer company, and commodity are called SARTOMER 239B.

Other preferred aspects according to the present invention, this monomer comprises the reaction product of trivalent alcohol and vinylformic acid reagent.Wherein this preferred trivalent alcohol comprises TriMethylolPropane(TMP).The example that is used for the reaction product of the trivalent alcohol of plastisol composition 28 and vinylformic acid reagent is a trihydroxy methyl propane trimethyl acrylate.This material is a commercially available product, is produced by Sartomer company, and commodity are called SARTOMER S-350.

Read after the disclosure, other suitable acrylate monomers will be open-and-shut for persons skilled in the art.

E, product performance

Though the applicant is not intended to sincerely believe in or is limited to any specific theory of operation, it is believed that the formation of the interpenetrating polymer networks that comprises the decoration primitive of being inlayed basically, be the major cause that forms premium properties of the present invention and feature.Specifically, the formation of interpenetrating polymer networks, particularly preferred IPN of the present invention as decorating the material that primitive embeds, is played significant feature to the peculiar bad fringe phenomena of avoiding prior art occurring of method.For example, the applicant thinks, causing product of the present invention to show the major reason of excellent feel, is owing to used a kind of first polymkeric substance that contains thermoplastic resin, and with this thermoplastic polymer IPN and pierce the IPN of a kind of thermosetting polymer of its inside.More particularly, the applicant finds, polymeric constituent according to the described mode of the disclosure with combine under its defined terms, is made the embossing product possess a kind of people and exploring but up to successful tensile strength and the balance between extending always.

The anti-rolling of product of the present invention is pressed to fall into and preferably is not more than about 5 mils, more preferably no more than about 4 mils, most preferably is not more than about 3 mils.It is a kind of like this performance that the anti-pressure of rolling falls into, it is an important indicator of weighing the wearing layer quality that is used for ground and wall surface lining, because on behalf of a kind of wearing layer opposing, it move the ability of the surperficial tension set that causes along the surface owing to the furniture such as chair with castors and desk.It is at first to stipulate a mobile route that the measuring method that falls into experimental result is pressed in the anti-rolling that this paper provides, for example a circular trace.Then, mark 7 points, measure the original depth of above-mentioned every bit place sample along this track.With one be equipped with 3 castors, each castor load is that 100 pounds equipment moves along this projected path, makes each castor all slip over whole track simultaneously.After castor slips over, measure the thickness of this product at 7 predetermined point places.Then, second sample to identical product repeats same test.Then, deducting the final thickness of each sample at each some place from each sample in the original depth of each point, is the result that unit averages and falls into as the anti-pressure of rolling with mil (0.001 inch).

Further preferably, the Stiletto resistance to compression of product of the present invention falls into and is not more than about 10 mils, more preferably no more than about 9 mils, most preferably is not more than about 8 mils.It is the tolerance that a wearing layer is tolerated the relative capacity of tension set after the effect that stands Stiletto heel (heel) that the Stiletto resistance to compression falls into.The measuring method that the Stiletto resistance to compression that this paper provides falls into numerical value is, allowing product sample stand to be added in diameter is to last about 10 seconds under 150 pounds of loadings on 0.5 inch the spheroid.The test program be, prepare one the 2 inches flooring products samples of taking advantage of 6 inches, on sample, mark 3 test point then.The thickness of the Randall Stickney gauge measurement flooring products sample of 1/4 inch flat pin at each test point place is equipped with in employing.Steel ball by one 0.5 inch on each test point applies 150 pounds loading, keeps for 10 seconds.Then, wait for 1 hour and allow sample recover that after 1 hour finished, the residual pressure of measuring each test point place with 1/4 inch hemisphere face gauge fell into the degree of depth from loaded state.Then, deduct final pressure and fall into thickness from the original depth of each test point, unit is a mil, asks the result's of this three place mean value, falls into numerical value as remaining resistance to compression.

Preferred product of the present invention also has splendid balance between tensile strength and the elongation.Specifically, product of the present invention preferably has than higher draw tensile strength, this sign that is this product aspect anti-permanent and quality, and it also has than higher stretch value simultaneously, and this is again an ideal very from the angle of laying.According to particularly preferred embodiment, the tensile strength that veneering products of the present invention has is at least about 30 pounds, more preferably at least about 45 pounds, most preferably at least about 50 pounds.Equally preferably, the elongation that flooring products of the present invention has is greater than about 25% and less than about 60%, and more preferably about 30%-is about 60%, most preferably is about 45%-about 55%.

Tensile strength that this paper provides and elongation numerical value are that to adopt model be that the Dilman tester of Motorized M1 is measured.Prepared to be of a size of 1 inch and taken advantage of 1/32 inch flooring material sample of taking advantage of 5 inches, the long limit of sample is parallel to the machine direction of sample.Then top wearing layer is peeled off out from bottom.Then to wearing layer test, way is after according to the standard program calibration, is placed on spacing on the tester and is between 1 inch the upper and lower anchor clamps.Make equipment with the about 12 inches full-speed operation of per minute, other conditions are according to standard program.Power when being the unit record fracture with the pound is as tensile strength.According to the Standard operation procedure SOP of this Dilman tester, measure elongation roughly the samely, the result who obtains is for being the stretch value of unit with the inch.The numerical value that will be unit then with the inch is multiplied by 100, promptly as elongation.

Product of the present invention also preferably has and is not more than approximately 600, more preferably no more than 500, most preferably is not more than 450 Taber stiffness.The Taber stiffness numerical value that this paper provides is that to adopt model be that the Taber stiffness tester of 150-B or 150-D is measured.This test adopts the 2-3/4 inch to take advantage of the sample of 1-1/2 inch, and its longer sides is parallel to machine direction.Because temperature and humidity is influential to stiffness, thus with sample controlled condition (73 °F+/-2 °F, 50%RH+/-4%RH) indoor 6 pounds weight flattens placement 24 hours.Test and weight was removed from sample in preceding 1 hour.The operation of testing apparatus is carried out according to standard program, wherein angle switch is set in 15 °.Get " right side " with " left side " mean value of reading.According to pendulum weight as shown in the table, respectively the result is multiplied by different coefficients, thereby records final Taber stiffness value with the expression of half Taber stiffness unit (TU/2).

Pendulum weighted average reading multiply by:

Do not have 0.5

125 0.62

250 1.25

500 2.5

1,000 5.0

2,000 10.0

II, method

The preparation of A, reactive matrix

Usually, the present invention requires at substrate upper berth one deck reactive adhesive, simultaneously on this reactive adhesive surface or inside contain the decoration primitive.For simplicity, this paper is referred to as to be filled with reactive matrix of particulate or reactive adhesive matrix to whole layer sometimes.Here employed " reactive adhesive " speech refers to certain tackiness agent or adhesive composition, and it comprises can react the reactive component that forms polymkeric substance, multipolymer and/or polymer network.According to the most preferred embodiment, reactive adhesive comprises reactive plastipaste, preferably is made of it basically, more preferably is made of reactive PVC plastipaste basically.Here employed " reactive plastipaste " speech refers to a kind of plastisol composition that comprises above-described reactive monomer or oligomeric material.

Generally preferably, decorate primitive and be embedded in basically among the reactive bonding agent material, but notice yet, in certain embodiments, certain part at least of decorating primitive may not reach reactive adhesive.For example, in certain preferred aspects, the part of some decoration primitive is exposed to outside the wearing layer end face at least, thereby does not contact with reactive adhesive.In a word, for the purposes of the present invention, this decoration primitive is considered to be embedded among the hypothallus basically.

Expect within the scope of the present invention, having various ready-made technology to be filled with particulate reactive adhesive hypothallus so that on substrate, add for utilizing.For example, be placed on a kind of making in suitable blending machine or other mixing devices and reactive binder composition blending simply, distribute uniformly, just belong within the scope of the invention to realize decorating primitive basic in reactive adhesive with decorating primitive.Can adopt traditional coating apparatus will be dispersed with the reactive adhesive coating of decoration primitive, or adopt other modes to impose on the suitable substrate.But, in this class embodiment, preferably, adopt contrary roll-coater to apply and be filled with the particulate plastisol composition.No. the 5th, 178,912, the United States Patent (USP) of Piacente, this patent has transferred transferee of the present invention and has received people this paper as a reference, discloses such technology.

Belong to also having in the scope of the invention, coating one deck reactive adhesive on substrate is decorated primitive at this reactive adhesive surface deposition then earlier, thereby adds that such one is filled with the reactive layer of particulate.Perhaps because the decoration primitive sinks to reactive adhesive and/or because the procedure of processing of carrying out later on makes that decorating primitive is embedded among the reactive adhesive layer basically.To be described with reference to the accompanying drawings a kind of like this method hereinafter.

Reactive adhesive of the present invention preferably contains following composition: thermoplastic polymer, the softening agent that is used for this thermoplastic polymer and reactive component.Thermoplastic polymer and softening agent are preferably selected according to technology above-mentioned.In addition preferably, reactive adhesive of the present invention not only comprises reactive monomer or the oligopolymer of pointing out above, but also contains the catalyzer that is useful on these reactive compounds.In especially preferred embodiment, the polyvinyl chloride plastisol composition that thermoplastic polymer and softening agent comprise a kind of fluidised form together, can be coated with, reactive component then comprises reactive thermosetting monomer and is used for this monomeric catalyzer.

Expect various kinds of catalyzer are arranged applicable to this preferred reactive plastipaste.And preferably, this catalyzer comprise a kind of can the monomeric polymerization of catalyzed reaction when being exposed to hot conditions and/or the thermocatalyst of crosslinking reaction.

The applicant finds that some catalyzer usually is not suitable for according to purposes of the present invention, and other catalyzer are then very suitable.Though do not intend sincerely believing in or be limited to any specific theory of operation, the appearance that it is believed that this species diversity is because some catalyzer can be by the polyvinyl chloride resin deactivation.Therefore, according to the preferred embodiment that the applicant finds, it is to have peroxide (O-O-) Bu Fen compound that the catalyzer of use preferably includes feature.Expecting has diversified peralcohol catalyzer can be used for reactive plastisol composition of the present invention, comprises alkyl peroxide, for example di-t-butyl peroxide and dicumyl peroxide, and peroxy esters compounds.Here said peroxy esters compounds, refer to a kind of with contain-C (=O)-O-O-partly is the compound of feature, peroxidized t-butyl perbenzoate and peroxide-2-tolyl acid tert-butyl ester for example.The inventor finds that the peroxy esters catalyzer is the preferred catalyst that is used for the inventive method.Peroxidation phenylformic acid tertiary butyl ester is particularly preferred, and the commercially available prod supply is arranged, and commodity are called ESPEROX10.

The catalytic amount that adds reactive binder composition should preferably enough polymerizations of this plastipaste of initiation and/or crosslinked when being exposed to high temperature and pressure, as what below will explain in more detail.

The applicant finds that for embodiment of the present invention of using reactive PVC plastipaste as reactive adhesive, polyvinyl chloride resin wherein is to the ratio particularly important of reactive component.Specifically, the applicant finds, if polyvinyl chloride resin to reactive acrylate's ratio not within limits, then can not get according to unusual between each physicals of the present invention and unusual Ideal Match.More particularly, the applicant finds that the PVC in the reactive plastipaste of the present invention: reactive acrylate's weight ratio is preferably about 2: about 5: 1 of 1-, more preferably about 3.5: about 4.5: 1 of 1-.

Reactive PVC plastipaste binder composition of the present invention preferably contains the polyvinyl chloride resin of about 50 weight parts of the 35-that has an appointment (pbw), the more preferably from about about 45pbw of 35-.Reactive plastipaste also preferably contains the softening agent of the about 12pbw of 8-that has an appointment, the more preferably from about about 11pbw of 9-.Reactive plastipaste also preferably contains the reactive acrylate of the about 12pbw of 8-that has an appointment, the more preferably from about reactive acrylate of the about 11pbw of 9-.And, in reactive PVC plastipaste binder composition, preferably contain the catalyzer of the about 0.5pbw of 0.2-that has an appointment, more preferably from about 0.3pbw.

Comprise multi-functional acrylate's monomer and be used for this monomeric embodiment of crossing oxygen catalyst for the reactive component of reactive plastipaste wherein, reactive plastisol composition preferably contains the mistake oxygen catalyst that the polyvinyl chloride resin of the about 45pbw of 35-that has an appointment, the about 10pbw of about 8-are used for reactive monomer and the about 0.3pbw of about 0.2-of the softening agent of polyvinyl chloride resin, the about 12pbw of about 8-.

Pressing solidly of B, matrix

Deposit to for the embodiment on the reactive adhesive coating for decorating primitive, method of the present invention preferably includes the step that reactive matrix is pressed solidly.Though as mentioned above, the decoration primitive of matrix just may be embedded among the reactive adhesive after matrix is shaped at least in part, preferably, matrix is pressed solidly, thereby makes it densification, also preferably matrix is pressurizeed.The effect of this process is to guarantee that particle embeds to greatest extent, and the more important thing is, eliminates or significantly reduces undesirable hole in the binder matrix layer at least.

Therefore, the operation that presses solidly of the present invention preferably includes, and allows reactive matrix acceptance be enough to the processing that makes particle be embedded in the binder matrix basically and make time, temperature and the pressure condition of hypothallus densification.Preferred condition comprises, places about 150-about 350 pounds/square inch (gauge pressures) (psi) under the effect of pressure reactive hypothallus.This processing can comprise upward plain roll of pressure drum and pressurization by any realization in some any means known.

In some embodiment preferred of the present invention, press solidly and be divided into two or more stages and finish.This method that presses solidly stage by stage is particularly preferred for the embodiment that decoration particle is deposited on the reactive adhesive coating.Specifically, concerning this method preferably, press solidly in the step the pressurization of reactive adhesive matrix first, preferably make to be loaded with to contain the add drum pressure of particulate binder matrix by heating, this adds drum pressure preferably applies the about 300psi of about 150-to matrix pressure.This operation not only makes matrix begin the process of pressing solidly, and guarantees that decoration particle embeds in the tackiness agent fully.Preferably binder matrix is applied higher pressure then in the stage that presses solidly of back.

The stage of pressing solidly of back preferably includes, and matrix is sent into plain roll in one or more pressurizations, and preferably will pressurize and go up the plain roll cooling.The pressure that plain roll is executed this product in the pressurization is preferably about the about 350psi of 330psi-.

The gelation of C, matrix and plasticizing

Press solidly in the embodiment at preferred multistage, first press solidly with gelation stage by following such in greater detail, finish together by the heating and pressurizing drum.

Known, fluidised form PVC plastisol composition comprises liquid plasticizer and the polyvinyl chloride resin dispersion or the suspensoid that are dispersed in this softening agent.As well-known to those skilled in the art, the non-reacted fluidised form plastisol composition of Shi Yonging must could obtain the satisfied wear resisting property that resiliently-mounted floor requires through processing in the past.Non-reacted fluidised form plastipaste heating is caused that usually plastipaste is in the physical change aspect the rheology.In other words, this fluidised form plastisol composition will experience or enter the gel phase state along with its temperature is enhanced sufficiently high degree.

For simplicity, this paper shows pre-gelled from plastipaste near the stage with " gelling temp scope " vocabulary, and perhaps plastipaste viscosity begins to raise near the point, until near this section temperature the gelation point.About the determination techniques of the gelation point of any specific plastipaste, known to those skilled in the art and can obtain.For example, can adopt a kind of gel slab that only at one end heats, form the thermograde of the end to end of slave plate thus.When being poured over the fluidised form plastisol composition on this plate, that the plate temperature that plastipaste loses its flowability is the gelling temp or the gelation point of alleged usually this plastipaste.

The gelling temp scope of any specific plastipaste is the function of multiple variable, comprises the kind and the relative populations of the softening agent-resin that contains.Yet according to general deduction, the gelling temp scope of fluidised form plastipaste of the present invention will appear at about 150 °F-Yue 340 °F, preferably about 280-Yue 340 temperature range.After gelation was finished, plastipaste generally was that do, strong relatively basically solid.

Generally preferably, make binder matrix gelation of the present invention and plasticizing.As well-known to those skilled in the art, this gel that contains softening agent and polyvinyl chloride resin can plastify after being heated to enough degree.Specifically, know, plastipaste is heated to substantially exceeds its gelation point and can make plasticizer molecule begin to change into and PVC polymer molecule bonded state, so " plasticizing " just begun.Along with proceeding of heating, softening agent and PVC polymkeric substance can become one basically.In this state, this plastipaste just has been known as " plasticizing plastipaste ".Adopt " plasticization temperature scope " this term to represent the temperature range that plasticizing process takes place, say that typically this is a temperature range that roughly begins more than gelation point.In many embodiment preferred, this plasticization temperature scope is higher than about 280 °F.

In certain embodiments of the invention, be filled with the reactive matrix of particulate and can improve by temperature that simply will this layer and keep one section to be enough to take place gel and plastifying time, make it gel and also plastify.In these embodiments, can be by the product by heating that will press solidly to about 325-Yue 470 temperature and keep about 1 minute-Yue 6 minutes time to realize plasticizing.Preferably, according to the character of used concrete polymer materials, with product by heating at least about 385 temperature.For example, this can be by allowing this layer finish by the plasticizing stove.

Should be understood that as described hereinly press solidly, gelation and plasticizing step be not necessarily in moment with take place respectively.On the contrary, in certain embodiments preferably, press solidly, gelation and plasticizing realize stage by stage, and the step of two in these steps or more multistep can overlap each other with a step or the multistep in other various steps.For example preferably, the effect by the pressure and temperature that allows matrix stand simultaneously basically to improve makes matrix at least both begin to press solidly and also begins gelation process.For example, this can adopt the heating and pressurizing drum to realize.Decorated primitive and be dispersed in embodiment in the middle of this tackiness agent in advance for impose on moment on the substrate at reactive adhesive, the main purpose of utilizing the heating and pressurizing drum to pressurize is the aspect press polish.And on the other hand, be deposited to for the embodiment on the reactive adhesive coating for decorating primitive, then than higher, be preferably about 150psi-300psi by heating and pressurizing drum applied pressure, and the purpose of pressurization is not only for press polish, and is in order to press solidly.Under latter event, gelation and pressing solidly at least begins basically simultaneously.And, expect in certain embodiments, in the heating and pressurizing drum, also may begin to take place the plasticizing of softening agent and polyvinyl chloride resin.This shows, in an independent equipment, press solidly, gelation and these three steps of plasticizing all may take place to a certain extent.

The polymerization of D, reactive matrix

Important and crucial is that method of the present invention requires to make the reactive component polymerization of reactive matrix.And, comprise non-reactive polymer, for example polyvinyl chloride resin basically for reactive matrix, and the embodiment of reactive component, especially preferredly be, present method comprise make reactive component in the existence of non-reactive polymer down to the small part polymerization, thereby form IPN.It is believed that this preferred way plays a part decoration primitive " locking " in polymeric matrix, thereby to realizing that the every advantage relevant with the present invention has important contribution.

According to some embodiment preferred, the polymerization of the reactive compounds of part before finally pressing solidly, wearing layer just takes place at least.A kind of like this process, for example can by to two sections of this layer branches or more multistage apply consolidation pressure and finish, wherein the last period, applied pressure was lower than the pressure of several sections of back one section or backs.Like this, mosaic coating is just because reactive compounds polymerization at least in part, thereby obtains at least in part just to be exposed under the highest consolidation pressure after the premium properties of the present invention.

As what those skilled in the art understood, the plastisol composition of decorating primitive that contains in the past requires hypothallus is carried out pressing solidly under heat and pressure condition.Mention above, in this procedure, occur decorating the striped and the elongation phenomenon of primitive sometimes just.Yet the applicant finds, thisly do not wish that the phenomenon that takes place can be avoided basically by the preferred method of the present invention, because method requirement of the present invention, in pressing solidly step, polymerization has at least partly taken place the reactive component of reactive adhesive.This preferable methods plays a part to cause the IPN forming process at least, like this, can not make under the pressure that the binder matrix layer stands during pressing solidly usually and decorate primitive elongation or distortion.

According to especially preferred embodiment, the applicant finds, it is essential, the reactive component of selected reactive plastipaste, should be able to reactive matrix be exposed to press solidly the peak pressure that the step mesostroma stands before, begun polymerization at least.For the preferred multistage of the present invention presses solidly step, preferably began polymerization in the past in the final stage that presses solidly at least, more preferably just begin polymerization in the initial stage that presses solidly.

The applicant also finds, before preferably the polyvinyl chloride resin in plastipaste plastifies fully at least, more preferably beginning basically before the plasticizing, and the reactive component of reactive matrix just begins polymerization.

Cause according to polymerization of the present invention, can realize satisfactorily, also will be described in further detail this in conjunction with the accompanying drawings below by containing the reactive matrix of particulate with the processing of heating and pressurizing drum.

The explanation of III, embodiment example

Below, with accompanying drawings the preferred embodiments of the invention.

See the Figure 1A in the accompanying drawing particularly, what wherein draw is a rotatable feeding roller 10, send flat relatively, fiber or non-fiber-like substrate sheet or substrate 12 from roller 10, for example the fiber-like that constitutes by fiber overlapping, that intersect, that be generally asbestos or cellulose family, become felt or become the flat relatively sheet material of pad.Substrate 12 can be woven, non-woven, knitting or the textile materials of additive method manufacturing according to wish; Paper wood; Synthesize or synthetic plastic sheet or film; Perhaps for example at United States Patent (USP) the 3rd, 152,002,3,232,780,3,239,364,3,359,352 and 3,660, disclosed any material in No. 187.

At coating station 16, with a kind of base resin polymer composition 14, be preferably a kind of polyvinyl chloride (PVC) plastipaste, adopt for example contrary roll-coater, be uniformly applied to basically on the surface of substrate 12.

The thickness of base resin polymer composition or plastipaste 14, on the surface that is coated onto substrate 12 and in the Shang Weigan, basically be uniformly and be about 0.005 inch-Yue 0.060 inch, and if desired, perhaps necessary according to the requirement or the needs in future, even can be thicker.

Base resin polymer composition 14 is applied to the concrete means that adopted on the surface of substrate 12 does not involve core of the present invention, almost any suitable coating means all can be used.

Though the preferred synthetic resins that is used for base resin polymer composition 14 is the PVC homopolymer, many other Vinylites as described previously also can use.

Except that plastipaste, can also use organosol and aqueous latex, for example the water-sol (aquasols) and sol (hydrasols) adopt organic solvent and water respectively as dispersion or suspension medium simultaneously.

Other compositions of base resin polymer composition 14 can comprise, for example if wish to foam processing, the whipping agent such as azodicarbonamide; Various promotor/stablizers, initiator and catalyzer, for example zinc octoate, Lead Phosphite, Dibasic (Coated); Various heat and/or photostabilizer, for example metallic soap; Uv-absorbing agent; Tinting material, dye well pigment comprise titanium dioxide; Solvent and thinner, for example methylethylketone, methyl iso-butyl ketone (MIBK) and dodecylbenzene; Filler, for example clay and Wingdale; Viscosity modifier; Oxidation inhibitor; And fungistat and sterilant.

At base resin polymer composition 14 applied and adhere on the substrate 12 after, just product is put into and be maintained at about 240 °F-Yue 450 °F, in the stove of the temperature of preferred about 260-Yue 410 raising or 18 li heating of other suitable heating installations about 1 minute-Yue 5 minutes, thereby make composition generation gelation and hardening.Temperature and time is complementary, and temperature is high more, then the time short more, vice versa.Yet the temperature of this raising is not so high as to the whipping agent activation that makes in the prescription that may be present in base resin polymer composition 14 or decomposes so that this constantly just cause foaming,

Randomly, the finished product have pattern or decorative pattern if desired or required, can be subsequently at the stamp station 20 for the base resin polymer composition 14a stamp of gelation or hardening or add coating, what adopt is two pairs or

more printing rollers

22 and 24 to suitable engraving, uses the printing inks composition that comprises dyestuff, tinting material, pigment and so on.This printing inks composition can also contain synthetic resins, softening agent, stablizer, oxidation inhibitor, and the surface effect of concavo-convex if desired or required or band texture contains foaming control agent in the zone of selecting.The drying of the printing inks composition that stamps adopts dry air or traditional heating-exsiccant step to finish.

In certain embodiments, the foaming effect that the base resin polymer composition 14 of potential foaminess is arranged is so strong or violent, so that wearing layer or other layer of its top are often gone out and attempted to enter to whipping agent generation or the gas that discharges from the base resin polymer composition that is heated, thereby the smooth finish and the planarization on wearing layer surface produced adverse influence.If the desirable just characteristic of surface smoothness and planarization, then this can be fatal problem, and, see it is unfavorable from angle attractive in appearance.

This unfavorable effect can be avoided like this: before or after the base resin polymer composition is printed on decorative pattern or pattern, yet before adding further coating or stratiform thing, on composition 14, add a relatively thinner barrier coat or a stratiform thing, its thickness has only about 6 mils or thinner, even is as thin as about 1 or 2 mils.This barrier coat or film can prevent effectively gas from the base resin polymer composition that is foaming towards top escape.

This barrier coat can adopt form of film, but generally is that plastipaste or resin polymerization compositions with the thin resin layer form such as the higher multipolymer of polyvinyl chloride or molecular weight is coated with up.This barrier coat is gelation thereupon under the temperature of the raising that is lower than whipping agent activation or decomposition temperature naturally.Figure 1A roughly expresses typical sealing coat coating station 25.

Be two kinds of typical sealing coat formulation for coating material below:

Umber ^*Umber ^*Polyvinyl chloride, high molecular, the dispersion liquid level, limiting viscosity 1.4 89 90 polyvinyl chloride, high molecular, blending resin, limiting viscosity 0.9 11 10 dioctyl phthalate (DOP)s 6 epoxidized soybean oils 5 52,2,4-trimethylammonium-1,3-pentanediol diisobutyrate 6.9 8.8 butyl benzyl phthalates 29 19.6 (butyl benzyl phthalate) poly-dodecyl benzene 8.5 5.5Ba-Zn phosphate stabilizers 7.25 3 uv-absorbing agents 0.32 0.32 toner 0.01 0.01

^*The parts by weight of per 100 parts of resins, phr

Shown in accompanying drawing 1B, gelation resin polymerization compositions 14b advances to coating station 26 subsequently, at this, reactive plastipaste 28, promptly not dried, be clamminess, not gelation plastipaste, basically be coated on the surface of composition 14b equably, adopted, for example be immersed in the suitable coating roll 30 in traditional coating pan 32.

Just be applied on the base resin polymer composition 14b surface and the still not dried moment, the thickness of plastipaste 28 not dried, not gel is uniform substantially, is approximately 20 mils-Yue 26 mils.Can control by air doctor blade device 34 with against being coated with roller 36.This is the concrete means of the coating of gel, reactive plastipaste 28 and coat-thickness control not, and irrelevant with core content of the present invention, any basically suitable apparatus for coating all can use, as long as it can be coated with the thickness with control coating exactly.

This layer reactive binder composition 28, certainly be meant not gelation, uncured and plastifying not, its viscosity is (Brookfield) until up to 3500cps (Brookfield3 rotor from about 2500 centipoises (cps), 20rpm, 87-89 °F), above numerical value this plastipaste keeping itself not dried, the character that is clamminess and the condition of feature under effectively.

As what will will talk about below, this layer be not dried, be clamminess, the thickness of not gelation plastipaste 28 and viscosity thereof are that decision deposits to and sticking thereon decoration particle or one of factors of the quantity of debris layer and thickness metering and control.

Shown in Fig. 1 C, gelation resin polymerization compositions 14b and the not gel resin polymer composition layer 28 above it are then come forward and are decorated particle deposition apparatus 36.Resin polymerization compositions 14b and not gel resin polymer composition layer 28 cross a rotatable calibration roller 38, process fills the below of the hopper 40 of pelletizing, fragment and particle then, that this particle is layered on basically equably is not dried, be clamminess, the surface of not gelation plastipaste layer 28, in order to adhering subsequently and embedding wherein.

The preferred equipment that is used for to reactive adhesive supply particle 42 is not a part of the present invention, and the detailed U.S. Patent number 4,212 that is disclosed in of related content is in 691.

Along with below process and the continuation reach of tackiness agent plastisol composition layer 28 from flexibility envelope material scraper spare 54, the part of the supply storing of ornamental particle or fragment 42 deposits equably basically and adheres to thereon.Decorate particle or fragment and preferably according to particle the binder wt ratio is about 1.5: the ratio that 1-is about 2.0: 1 is layered on above the plastisol composition 28.More preferably according to about 1.8: 1 weight ratio.

Decorate similar while of particle or fragment or and then in deposition, substrate carrier 12, carry gelation resin polymerization compositions 14b and above it not dried, be clamminess, gel plastipaste resinous polymer composition layer 28 not, enter with the bed board 46 that tilts and be the sliding contact state, be guided forward, moving upward by the mode of forcing to drag then.

Above near inclination bed board 46 upper ends, be provided with a reverse rotation hired roughneck 56 with radially-protruding tooth or blade, it impacts the back side of carrier substrates 12 discontinuously, thereby make it shake or vibration, like this, landing or the part fallen adhere to, adhere to insufficient or laxly the decoration particle or fragment 42 just was not released again and landing as yet before all this, get back to supply with in the storing and go, so, have only adhere to firm decoration particle or fragment still stay not dried, be clamminess, gel plastipaste 28 surfaces not.

With back substrate 12, carry on gelation base resin polymer composition 14b and its not dried, be clamminess, gel plastipaste resin polymerization compositions 28 and be bonded at decoration particle or chip material above it not, continuing obliquely, the side advances, cross rotatable deflector roll 58, further processing or precision work are sent in preparation, comprise press solidly, gelation and plasticizing, this partial content will be done below more fully and discuss.

Above said further processing or finishing operations can take multiple different form and relate to multiple multi-form equipment.Fig. 1 D represents a kind of so further processing, wherein expression is first section that a kind of multistage presses solidly process, it adopts the garden the turned round cylindrical drums of large-scale steam heating (or superheated vapour heating), can be heated to 400 or higher high temperature, so that begin the process of pressing solidly.Generally preferably, through being exposed to such heating drum, the temperature of binder matrix is elevated to about 300-310 °F.This also is gel section and multi-stage polymeric first section.

Round the periphery of this heating drum, a plurality of heating, rotatable, pressurization cylinder pressure roller 62,64,66 and 68 are arranged, they can be exerted pressure to any material that is placed on the periphery that heats cylinder drum 60.Between heating cylinder drum 60 and each backer roll 62,64,66 and 68, can adopt contact pressure up to about 300psi.

The applicant finds, particularly preferably is, and is just beginning with after heating drum 60 contacts, and allows the binder matrix on the product 70 stand lower pressure, preferably is not more than the pressure of about 200psi.Like this, matrix be subjected to lower consolidation pressure during wherein reactive component just begun polymerization.For accomplishing this point, for example can apply lower pressure to backer roll 62 and 64, for example 150-200psi applies higher pressure to backer roll 66 and 68 simultaneously, the about 300psi of for example about 250-.Like this, with regard to the pressure period of adopting different pressures, first section of pressing solidly itself is exactly a multiple segment procedure.Because the preferred residence time that binder matrix is centered around on the heating drum 60 is about 60 seconds of about 20-, this has just reserved about 30 seconds time of about 10-and has caused for carry out polymerization under lower consolidation pressure condition.

So, the substrate 12 that carries base composition 14b and plastisol composition 28 experiences one section time enough under the temperature and pressure condition that is caused by heating drum 60 and backer roll 62,64,66 and 68, so that the polymerization of the reactive component in (1) initiation reaction plastipaste at least basically side by side, and (2) make and are filled with particulate plastipaste layer and begin at least to press solidly and gelation process.According to embodiment preferred, drum 60 is heated to about 315 temperature of about 295-with binder matrix, more preferably from about about 310 temperature of 300-.In particularly preferred embodiments, cylindrical drum 60 makes the temperature of matrix reach about 305 °F.The applicant finds that such preferred method can make reactive plastipaste begin to be converted into IPN at least.That is to say, make reactive component polymerization in the presence of polyvinyl chloride resin and decoration primitive according to method described above to containing the reactive layer heating of particulate and/or adding pressure energy, preferably take place crosslinked, from and make at least and begin to form preferred interpenetrating polymer networks.Yet, should be appreciated that the further reaction between reactive component preferably occur in the procedure of processing of back, for example in wearing layer plasticizing step.In these implementation steps, IPN is networking further, thereby makes superiority of the present invention obtain to embody fully.

Allow matrix accept the not only polymerization of preferably initiation reaction component of heat of drum 60, and cause plastipaste gelation at least in part, more preferably gelation fully basically.

When preferably beginning polymerization and gelation, method of the present invention also preferably includes the process that initially presses solidly of binder matrix layer.This stage that initially presses solidly mainly realizes by a plurality of heating, rotatable pressure roller 62,64,66 and 68.

Initially press solidly in the stage at this, along with product 70 circumferential motion along drum, it is exerted pressure improves constantly, and preferably makes decorative surface stand the pressure of the about 300psi of about 150-.Preferably, the pressure that allows combination with decorative surfaces stand in the fs that presses solidly is no more than about 300psi.

Thereby the substrate after not condensing, being coated with between drum 60 and backer roll 62,64,66 and 68 by partly solidified and press solidly the needed time, can select according to the result of hope, except that other parameters, it is relevant with the temperature and pressure of the character of resin combination and thickness and employing.Preferably, allow not the gel substrate lasts about 20 seconds under the temperature and pressure of above-mentioned preferred raising-Yue 40 seconds, more preferably last about 25 seconds-Yue 35 seconds.Preferably, allow the substrate after pre-gelledization, the coating under the temperature and pressure of above-mentioned raising, last about 30 seconds, so as to finish partially polymerized, part presses solidly and fully gelation basically.

Press solidly one of the result in stage as this, obtained the resinous polymer sheet material 70 that partly presses solidly, wherein, decorating particle or fragment 42 is embedded among the not gel plastipaste 28 not dried, that be clamminess, thereby form harder, the slick particulate plastipaste that is filled with of surface ratio, it is combined in above the basal layer resin polymerization compositions 14 securely, is lined with carrier substrates 12 below the latter.

Then, to gelation, part press solidly, partially polymerized matrix 70 preferably processes, make it to press solidly fully, if require or wish also plasticizing fully.According to material, the plasticizing fully of plastipaste can be owing to sheet material 70 is exposed under the high temperature in the plasticizing stove (not shown) that a kind of flooring material industry generally uses simply takes place.In embodiments of the invention, preferably, reactive plastipaste matrix is plasticizing fully basically, and reactive component wherein is polymerization fully basically.Plasticizing in this case is normally by being heated to product 70 about 325-Yue 470 temperature, and keeps about 1 minute-Yue 6 minutes time to realize.Character according to the polymer materials of concrete use preferably is heated to product 70 temperature at least about 385.If contained whipping agent in the base resin prescription, the temperature of such raising also is enough to cause in the inner foaming of base resin polymer composition usually.Foaming all may occur in any He all zones that do not have the adding owing to suds suppressor that the effect of whipping agent is suppressed, this suds suppressor is some zone that is added in the selected part of required printing pattern or pattern with the printing inks composition.

But, in a more preferred embodiment, press solidly, polymerization and plasticizing be to finish according to technology stage by stage such shown in Fig. 1 E.According to a kind of like this technology, gelation, part press solidly, partially polymerized product 70 is admitted to a stove that comprises a series of infrared heating sources shown among Fig. 1 E 80.This step is then preferably further brought up to about 370 °F with the temperature of binder matrix layer, makes the further polymerization of reactive component.Preferably, because product 70 is placed into stove 80, has also begun the plastipaste plasticizing at least and be the process of polyvinyl chloride resin.

Go up between the plain roll 81 by pressurization subsequently from the part plastifying product 70 that stove 80 comes out, at this, binder matrix gas producing formation 70 stands pressing solidly of subordinate phase.Preferably, press solidly the stage adhesive hypothallus second and stand the about 350psi of about 320-, the more preferably from about pressure of the about 350psi of 330-.Also preferred, it is that plain roll is gone up in the refrigerative pressurization that plain roll 81 is gone up in this pressurization.

Leave the product of going up plain roll 81 that pressurizes and then be imported into gas-fired radiation stove 82, in this stove, binder matrix is plasticizing and polymerization fully preferably.According to embodiment preferred, plasticizing and polymerization stage that this is final comprise that allowing binder matrix heat is enough to realize basically plastifying fully and the polymeric time under about 320 temperature of about 270-.The applicant finds that this time was preferably about 1-about 4 minutes.

Yet choose wantonly also preferably, the product 70 that leaves stove 82 stands the processing that plain roll 83 is gone up in second group of pressurization again.When plain roll 83 partly played the effect that further presses solidly binder matrix gas producing formation 70 in pressurization, this pressurization was gone up plain roll and is preferably also comprised impression cylinder, extruded the decorative pattern or the pattern of wishing on the surface of product 70.

In the process segment of plain roll 83 in pressurization, the binder matrix layer also preferably stands the about 350psi of about 320-, the more preferably from about pressure of the about 350psi of 330-.

Then, these the finished product advance to rotatable wind-up roll 84, so that machine is deposited or further processed and handle according to hope or requirement down.

The present invention will further be described in conjunction with the following explanation example of the present invention that is mainly used in.

Example I

Signal is used to finish following process with the equipment that roughly draws among Fig. 1:

Fiber reinforced sheet material or substrate comprise by become felt and do not have that the fibrous magnesium silicate of photochemical (felted and matted) is formed, be flat, 0.040 inch thick fibre plate relatively, its surface has the smooth finish of acrylic coating.

The basic resin type of coating, potential foamable polymer composition on substrate, for example PVC plastipaste accomplishes that wet thickness is even substantially.Gelation and sclerosis take place in this potential foaming base resin polymer composition about 3 minutes time of process in about 300 process furnace.Then, stamp decorative pattern or pattern on gelation, hardened PVC plastipaste, hope is coated with barrier coat then on the surface of this PVC basal layer, makes coat-thickness reach about 3 mils.

Then, in this stamp, gelation and sclerosis and add on the basal layer plastipaste of barrier layer, be coated with again one deck not dried, be clamminess, gel PVC plastipaste resinous polymer composition coating not, said composition contains: about 33% (weight) pearl filler, about 9% (weight) butyl benzyl phthalate softening agent, about 40% (weight) PVC homopolymer resin and about 10% (weight) SARTOMER350.This PVC homopolymer resin be contain in the mixture of 80% (weight) dispersion resin and 20% (weight) suspending resin in-low-molecular-weight resin.This dispersion resin is by the supply of Occidental Chemical company, and commodity are called 688C, and this suspending resin is by the supply of Borden company, and commodity are called R501.Weight with SARTOMER350 is benchmark, and this reactivity plastipaste also further contains the ESPEROX10 of 3% (weight).

Then, scribble not gelation of one deck, gelation base resin polymer composition not dried, the plastipaste that is clamminess is come a particle or fragment spreading station, at this, on it again basically equably the layer overlay resene decorate particle or fragment, the weight ratio of particle and tackiness agent is about 1.8: 1.Then, the substrate of having spread particle advances to the equipment of pressing solidly, for example at the equipment shown in Fig. 1 D, so that carry out partially polymerized at least and/or press solidly.

The temperature of main superheated vapour heating rotary drum is about 410 °F, and 4 rotatable backer rolls 62,64,66 and 68 pressure of being executed are respectively 150,200,250 and 300psi.The residence time of product on drum is about 30 seconds.

Pressing solidly in part/polymerization process in, decorate particle or fragment be pressed into and be embedded in not dried, be clamminess, gel plastipaste the inside not.Pressing solidly in part/polymerization process in, the part that the partially polymerized of SARTOMR350 is taken place basically simultaneously and contain the plastipaste of particle presses solidly.

Shown in Fig. 1 E, the product that part presses solidly moves on and comes a series of well heaters and the upward plain roll that pressurizes, and produces elasticity embossing flooring products at last.

Comparative Examples I

This example relate to need not reactive plastipaste tackiness agent typical prior art embossing flooring products.Program, composition and the equipment of employing described in example I has prepared the embossing veneer, and different is that the plastipaste tackiness agent is gone up substantially by about 13% (weight) pearl filler, about 26% (weight) softening agent and about 51% (weight) polyvinyl chloride resin and constituted.

Comparative Example II

Program, composition and the equipment of employing described in example I has been prepared the embossing floor, and different is that the plastipaste tackiness agent is gone up substantially by about 40% (weight) pearl filler, about 16% (weight) softening agent and about 32% (weight) polyvinyl chloride resin and constituted.

To testing according to the product for preparing in each example in the previous example, to measure following performance: tensile strength, elongation, resistance to compression fall into (remaining and rolling), delamination and Taber stiffness.These the results are shown in the following table 1.In this table, the result's of Comparative Examples I and Comparative Example II code name is respectively CEX.I and CEX.II.Give a kind of situation of selling well, competitive product, the i.e. CORLON that adopt the stencil printing technique to produce in the table 1 ^Test-results (CORLON ^Be the registered trademark of ArmstongWorld Industries company).

Table 1

The 150 pounds of Stiletto delamination Taber stiffness of rolling

Thickness hot strength elongation is pressed and is fallen into (1 hour/72 hours) (6000 times) (50F/73F) (%) (TU/2) the defective 245/205CORLON  of the defective 215/185CEX.II 84-86 of the qualified 500/420CEX.I 85-87 of example I 84-86 59-62 45-55 3.4 9.3/8.9 23-25 130-140 6.5 12.0/11.5 17-20 100-110 5.6 11.4/11.0 82-84 54-56 20-30 3.3 8.3/7.8 qualified 800/675 of (mil) (mil) (qualified/defective) of sample (mil) (pound)

Above-mentioned test-results shows, embossing veneer of the present invention according to tensile strength, elongation, resistance to compression fall into, delamination and stiffness wait and weigh, and has very ideal physicals.Compare with the typical prior art product (CEX.I and CEX.II) that does not use reactive matrix, veneer of the present invention have remarkable anti-ly open, elongation, resistance to compression falls into and performance such as anti-delamination.In addition, embossing veneer of the present invention has the feel that is better than the prior art veneer, prior art veneer, or too soft (CEX.I and CEX.II), or too stiff (CORLON ^).

Claims

1, a kind of method of making ornamental embossing flooring product comprises:

(a) during the manufacturing of product, be provided for supporting the substrate material of each layer above the product at least;

(b) the reactive plastipaste layer of surface construction on described substrate, described reactive plastipaste layer comprises reactive plastipaste and many discontinuous, ornamental primitives (decorative element), this ornamental primitive is embedded in described reactive plastipaste the inside at least basically, and described reactive plastipaste comprises Vinylite, is used for softening agent and a kind of reactive component of this Vinylite;

(c) make described plastipaste gelation;

(d) during described gelation step (c), make the polymerization at least in part of described reactive component; And

(e) by making the plasticizing fully basically of described reactive plastipaste, form wear-resisting embossing layer.

2, the process of claim 1 wherein that the step of the reactive plastipaste layer of described structure is included in the coating of the described reactive plastipaste of structure on the described substrate, and on described coating, deposit described ornamental primitive.

3, the process of claim 1 wherein that described ornamental primitive comprises ornamental resin particle.

4, the process of claim 1 wherein that described reactive component comprises the monomer that can aggregate into thermosetting polymer, and described Vinylite is about 2 to the weight ratio of described reactive component: about 5: 1 of 1-.

5, the method for claim 1, the step of the reactive plastipaste layer of wherein said structure is included in the coating of the described reactive plastipaste of structure on the described substrate, the ornamental primitive of deposition on described coating, and make described ornamental primitive be mounted to described plastipaste coating the inside basically to go.

6, the process of claim 1 wherein that described plastipaste contains the about 50pbw of the 35-that has an appointment (weight part) Vinylite, the about 12pbw softening agent of about 8-and the about 12pbw reactive monomer of about 8-.

7, the method for claim 7, wherein said plastipaste also contain the catalyzer that is used for the described monomer polymerization of catalysis of the about 0.5pbw of 0.2-that has an appointment.

8, the process of claim 1 wherein that described partially polymerized at least step comprises is heated to about 300 of about 200-with described reactive plastipaste.

9, the method for claim 8 wherein saidly partially polymerizedly comprises that the effect that allows described binder matrix stand to turn round heating drum (rotating heated drum) lasts about 40 seconds of about 20-.

10, the process of claim 1 wherein that described Vinylite comprises polyvinyl chloride (PVC) RESINS.

11, a kind of manufacturing has the method on the ornamental floor of embossing wearing layer, and it comprises the steps: to be provided for supporting at least the substrate material of this wearing layer during the manufacturing of product; Surface construction one deck fluidised form plastisol composition on this substrate; The ornamental resin particle of deposition is filled with particulate fluidised form plastipaste layer with formation on described fluidised form plastisol composition layer; Make this contain the plasticizing of particulate plastipaste layer then, thereby form the embossing wearing layer on this floor; The improvements of described method are that the following step poly-, and these steps comprise:

(a) make this plastipaste, make it to comprise the catalyzer that is used for the described monomer polymerization of catalysis of the about 50pbw Vinylite of about 35-, the about 12pbw softening agent of about 8-, the about 12pbw reactive acrylate monomer of about 8-and the about 0.5pbw of about 0.2-, form and be filled with the reactive plastipaste layer of particulate; And

(b) allow the described effect that the reactive plastipaste of particulate stands regular hour, temperature and pressure that is filled with, above-mentioned effect is enough to basically side by side (i) makes the polymerization at least in part of described reactive monomer, (ii) makes simultaneously and is filled with the gelation at least in part of particulate plastipaste layer; And

(c) by making described answering property of the particulate plastipaste that is filled with plastify and make described reactive acrylate monomer's polymerization fully, form wear-resisting embossing layer.

12, the method for claim 11 comprises and makes plastipaste, makes it to comprise the about 45pbw Vinylite of about 35-.

13, the method for claim 12 comprises and makes plastipaste, makes it to comprise about 41pbw Vinylite.

14, the method for claim 11, wherein said Vinylite comprises polyvinyl chloride (PVC) RESINS.

15, the method for claim 11 comprises and makes plastipaste, makes it to comprise the softening agent of the about 11pbw of about 9-.

16, the method for claim 15 comprises and makes plastipaste, makes it to comprise the softening agent of about 12pbw.

17, the method for claim 11, wherein said softening agent comprise butyl benzyl phthalate (butyl benzyl phthalate).

18, the method for claim 11 comprises and makes plastipaste, makes it to comprise the reactive acrylate monomer of the about 11pbw of about 9-.

19, the method for claim 18 comprises and makes plastipaste, makes it to comprise the reactive acrylate monomer of about 10pbw.

20, the method for claim 11, wherein said monomer comprises dimethacrylate 1,6-hexylene glycol ester.

21, the method for claim 11, wherein said monomer comprises trihydroxy methyl propane trimethyl acrylate.

22, the method for claim 11, wherein said catalyzer comprise peroxy esters (peroxy ester) catalyzer.

23, the method for claim 22, wherein said catalyzer comprise peroxidation phenylformic acid tertiary butyl ester.

24, a kind of elasticity embossing flooring products comprises an embossing layer, and this embossing layer contains interpenetrating polymer networks and many ornamental primitives that is embedded at least in part in the described interpenetrating polymer networks.

25, the embossing floor of claim 24, wherein said interpenetrating polymer networks comprises at least the first thermoplastic polymer and at least a thermosetting polymer.

26, the embossing floor of claim 25, the anti-rolling on wherein said floor presses sunken (rollingindentation resistance) to be not more than about 5 mils.

27, the embossing floor of claim 25, the Stiletto resistance to compression on wherein said floor falls into (Stilettoidentation resistance) and is not more than about 10 mils.

28, the embossing floor of claim 25, the tensile strength on wherein said floor are about 30 pounds at least, and elongation is greater than about 25% and less than about 60%.

29, the floor of claim 25, the anti-rolling on wherein said floor are pressed to fall into and are not more than about 5 mils, and the Stiletto resistance to compression falls into and is not more than about 10 mils, and tensile strength is about 30 pounds at least, extends to be about 25%-about 60%.

30, the embossing floor of claim 25, the Taber stiffness on wherein said floor is not more than about 600.

31, the embossing floor of claim 25, wherein said thermoplastic polymer comprises polyvinyl chloride.

32, the embossing floor of claim 31, wherein said polyvinyl chloride comprises the plastifying polyvinyl chloride.

33, the embossing floor of claim 25, wherein said thermosetting polymer comprises acrylic polymers.