CN109456726A - A kind of stone plastic floor muting pad is compound to use reaction type polyurethane hot-melt adhesive and preparation method - Google Patents
A kind of stone plastic floor muting pad is compound to use reaction type polyurethane hot-melt adhesive and preparation method Download PDFInfo
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- CN109456726A CN109456726A CN201811172342.6A CN201811172342A CN109456726A CN 109456726 A CN109456726 A CN 109456726A CN 201811172342 A CN201811172342 A CN 201811172342A CN 109456726 A CN109456726 A CN 109456726A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4202—Two or more polyesters of different physical or chemical nature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of stone plastic floor muting pad compound reaction type polyurethane hot-melt adhesive and preparation methods.This method uses polyester polyol, diisocyanate is basic raw material, it arranges in pairs or groups auxiliary agent, and makes 1.6~1.9:1 of molar ratio of isocyanate group and hydroxyl, reacted through high temperature polymerization and be prepared that stone plastic floor (SPC) muting pad is compound to use reaction type polyurethane hot-melt adhesive.Product of the present invention belongs to one-component moisture reaction type polyurethane hot-melt adhesive and sticks agent, is hardened without using crosslinking agent, instead is reacted with moisture with reactive NCO functional group to realize crosslinking by molecular resin chain end.Product of the present invention cohesive energy height has excellent initial solidification speed and then fastness, it is high to solidify after-tack fusing point, it is the bonding compound of TPE, EVA, non-woven fabrics etc. especially suitable for stone plastic floor (SPC) and mute cushion material, the floor SPC muting pad shrinking percentage is low after compound, heat resistance is excellent, dimensional stability is high, belongs to field of polymer material preparing technology.
Description
Technical field
The invention discloses a kind of stone plastic floor (SPC) muting pad compound reaction type polyurethane hot-melt adhesive and preparation sides
Method belongs to field of polymer material preparing technology.
Background technique
SPC:stone plastic composite, American-European countries are RVP (rigid vinyl this floor
), plank rigidity plastics floor.It is the epoch of a pursuit sustainable development now, new material new energy emerges one after another, SPC
Plate is a kind of floor decorative material of energy regeneration, this has the natural resources and ecological environment of protecting our earth huge
Big meaning.The floor SPC is the novel environment-friendly floor gone out based on high-tech development, has zero formaldehyde, mould proof, moisture-proof, fire prevention, prevents
The features such as worm, simple installation.The floor SPC is very popular in European and American developed countries and Asia-Pacific market, by its outstanding stability
And durability, not only solved the problems, such as that solid wooden floor board dampness deformation was gone rotten, but also the environmental protection such as formaldehyde for solving other finishing materials are asked
Topic, the requirement for having met domestic high-end customer are suitable for interior house ornamentation, hotel, hospital, the public places such as market.
Currently, the consumption concept of client is turning to the consumption of matter in the market, the domestic floor SPC Decoration Industry is quick every year
Increase, with the promotion of urbanization, the following decorative building material market can be very flourishing, and that adjoint at the same time is consumer of new generation
It generates, young and great-hearted consumer can be more biased towards in environmental protection, beautiful, economy the theory of design.Therefore, the floor SPC
House ornamentation is because excellent performance can be than other floors such as solid wooden floor board, stone floors currently on the market more by people blueness
It looks at.
Stone plastic floor SPC (Stone plactic composite) is to squeeze out PVC base by extruder combination T-die
Material, with three rollers or four-roll calender respectively PVC wearing layer, PVC coloured silk film and PVC base, one-time heating fitting, the production of embossing
Product, simple process.SPC is to belong to rigidity plastics floor, and sound-absorbing noise control effect is poor.It therefore in the prior art can be on the floor SPC
Compound one layer of muting pad below PVC base, improves sound-absorbing noise control performance, this mute cushion material is generally the foaming materials such as TPE, EVA
Material.
The floor SPC muting pad is compound at present uses two-component cold glue or pressure-sensitive glue laminating more, and two-component cold glue uses preceding palpus
It carries out to scale compound with being carried out after glue again, through a long time pressure maintaining is needed to can be only achieved enough fastness after compound.And the poly- ammonia of response type
Ester hot melt adhesive is not necessarily to pressure maintaining, can reduce manually leads to final product quality instability problem with glue, and production process is short, drop without matching glue
Low production cost.Pressure sensitive adhesive belongs to one-component solvent-free non-reactive hot melt adhesive, is good for the environment and keeps the safety in production, however it is lacked
Fall into mainly causes heat resistance and cohesive force insufficient without cross-linking reaction, and viscosity is affected by temperature more apparent, the compound good floor SPC
Through counter transport for long-distance high temperature action under and in hot environment in use, pressure sensitive adhesive stickiness reduction cause muting pad contraction distortion and
Degumming problem, to influence SPC floor quality.Therefore, improve there is an urgent need to a kind of instead colloid and promote the floor SPC
The quality of production.
ZL201610345746.5 discloses a kind of preparation of glutinous agent of composite floor board moisture reaction type polyurethane hot-melt adhesive
Method and application, belong to field of polymer material preparing technology.This method uses polyester polyol, diisocyanate, chain elongation
Agent is basic raw material, catalyst of arranging in pairs or groups, levelling agent, the auxiliary agents such as nucleating agent, through high temperature polymerization reaction at moisture reaction type polyurethane heat
Molten adhesive (PUR).Product disclosed in ZL201610345746.5 belongs to one-component moisture reaction type polyurethane hot-melt adhesive and sticks agent
Hardened without using crosslinking agent, instead by molecular resin chain end have reactive NCO functional group with
Moisture is reacted to realize crosslinking.Solvent misture is free of in ZL201610345746.5 basic material, which is only applicable to
Composite floor board surface layer and strengthening layer are then compound, are not suitable for, smaller scope of application compound with low polarity material TPE and EVA.Due to
Floor decorative material continuous advancement, past WPC floor use adhesive composite cover and strengthening layer, and the floor SPC is then by squeezing at present
Machine combination T-die squeezes out PVC base out, with three rollers or four-roll calender respectively PVC wearing layer, PVC coloured silk film and PVC base
The product that material fitting at one-time heating, is embossed reduces using adhesive composite cover and strengthens layer process.But SPC is to belong to just
Property plastic floor, sound-absorbing noise control effect are poor.Therefore it need to improve sound-absorbing noise control performance in the floor SPC compound one layer of muting pad again,
This mute cushion material is generally the foamed materials such as TPE, EVA.The special reaction that this patent product is invented by composite S PC muting pad
Type polyurethane hot melt adhesive.
Summary of the invention
To solve the problems, such as the existing floor SPC muting pad complex technique, the purpose of the present invention is to provide a kind of stone modeling ground
Plate (SPC) muting pad is compound to use reaction type polyurethane hot-melt adhesive, has excellent adhesive strength and heat resistance.The hot melt simultaneously
Glue is solvent-free, is good for the environment and keeps the safety in production, high production efficiency.
A kind of stone plastic floor (SPC) muting pad of the present invention is compound to use reaction type polyurethane hot-melt adhesive, is free of solvent, production
The solvent-free taste of process, no safety and environmental protection problem.It can be widely used in the mute material processing of plastic floor, processing is not required to dry
It is dry, it is not necessarily to pressure maintaining, speed is fast, and applicable base materials range is wide, and the compound rear floor SPC muting pad shrinking percentage is low, and heat resistance is excellent, size
Stability is high, can solve the problems, such as commercially available two-component cold glue and pressure sensitive adhesive.Stone plastic floor (SPC) muting pad of the invention is compound
It is rapid curing with the characteristics of reaction type polyurethane hot-melt adhesive, high initial bond strenght.According to the wet of ambient enviroment and substrate
Degree, the cross-linking reaction meeting last from days occurred after sizing, tensile strength is big after solidification and soft heat point is high, and imparting is gone out by then material
The bonding action and heat resistance of color.It is used after using muting pad laminating machine, solid gum to heat fusing in glue-smelting machine when use,
Heating temperature is 110~140 DEG C.The floor SPC is countries in the world today using a kind of extensive new terrestrial ornament materials, in Europe
U.S. market and Asia-Pacific market are very popular, and also very universal in China, development prospect is boundless.According to scholarly forecast, from now on
Reaction type polyurethane hot-melt adhesive will become the market mainstream within several years, fast-developing in the meeting of floor decorative material industry.For this purpose, this patent
There is provided that a kind of novel stone plastic floor (SPC) muting pad is compound with reaction type polyurethane hot-melt adhesive formula and to prepare the side of the resin
Method must make floor decorative material reach better quality product.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor (SPC) muting pad, including walk as follows
It is rapid:
S1, by polyol ester (polyadipate ethylene glycol butanediol ester, polyadipate -1,6-HD ester, poly- O-phthalic
The one or more of sour neopentyl glycol ester), after solvent misture, antioxidant metering in investment polymerization stirred autoclave, wherein polynary
According to properties of product and then, the characteristic of substrate selects one or more polyalcohols of arranging in pairs or groups to adapt to various differences for the selection of alcohol ester
Then, the antioxidant is Hinered phenols antioxidant, the total weight based on the polyurethane hot melt, antioxidant additive amount to substrate
For 0.1-0.3wt%.The solvent misture includes rosin resin or derivatives thereof, terpene resin or derivatives thereof, is gathered based on this
The total weight of urethane hot melt adhesive, solvent misture additive amount are 5-12wt%.
S2, the raw material heating polymerizeing in stirred autoclave is melted and is uniformly mixed, slow heating reaches material temperature
It 110-120 DEG C, vacuumizes and the vacuum degree in reaction kettle is down to 50torr hereinafter, then starting to be dehydrated, continuous negative pressure state 1-
Nitrogen charging replys normal pressure with moisture value contained by karl Fischer formula (Karl-Fischer) moisture teller detection material, if water after 3h
Score value reaches 300ppm (mg/kg) hereinafter, then terminating to be dehydrated, if moisture value is higher than 300ppm, returns to negative pressure state and continues to take off
Water；
Normal pressure is replied after S3, dehydration in reaction kettle, 80-90 DEG C is cooled the temperature to and is passed through nitrogen and maintain reaction kettle micro-
Positive pressure, the equivalent of consumption diisocyanate needed for calculating according to polyol ester molecular weight, the diisocyanate is MDI (hexichol first
Alkane diisocyanate) excess diisocyanate put into 1.6-1.9 times of polyol ester equivalent, reaction kettle is heated up and remains anti-
Answer 100-110 DEG C of temperature, the reaction time is not less than 2h, and (20-30min) detects isocyanic acid at regular intervals in reaction process
The weight percentage NCO% of ester group is added into reaction kettle when NCO% reaches theoretical value or less based on polyurethane heat
The catalyst of the total weight 0.02-0.1% of melten gel and the levelling agent of 0.10-0.30%, stir evenly and are warming up to reaction kettle
Bubble-free reaction terminates in 110-120 DEG C of negative pressure deaeration and sustained response to reaction kettle, and product appearance is colourless sticky to yellow
Shape liquid.The catalyst is that amine adds organic zinc class mixture, and levelling agent is acrylic acid esters co-polymer macromolecule.
S4, after completion of the reaction, obtains colourless to the sticky shape liquid product of yellow.
Preferably, in abovementioned steps S1, in one or more polyol esters, polyadipate ethylene glycol butanediol ester molecule
Amount is 2000-3000, and polyadipate 1, the molecular weight of 6- hexylene glycol ester is 3000-5000, poly- phthalic acid neopentyl glycol ester
Molecular weight is 700-1500.Total weight based on the adhesive for polyurethane, the content of one or more polyol esters are 70
To 80wt%.
These three above-mentioned alcohol esters can be made by oneself, can also be commercially available, and molecular weight meets the requirements.Molecular weight is by acetic acid
Acid anhydride-pyridine method is detected and is obtained, and the hydroxyl in sample and acid anhydrides quantify acetylization reaction, generates ester and acid, excessive acid anhydrides hydrolysis
After acid, is titrated with alkali standard solution, hydroxyl value can be calculated by blank and sample titrating solution difference.The definition of hydroxyl value is i.e.: every gram of sample
In contained acetylating hydroxyl groups when, the acid of consumption is equivalent to the quality of KOH (mg), is represented by mgKOH/g, is calculated by hydroxyl value polynary
Alcohol molecular weight:
Polyol molecular weight=2*56.1*1000/ hydroxyl value.With reference to examination criteria GB/T 12008.3.
Further, homemade polyadipate ethylene glycol butanediol ester, polyadipate -1,6- hexylene glycol ester, poly- adjacent benzene two
The preparation process of formic acid neopentyl glycol ester are as follows: put into synthesis material in reaction kettle, heating carries out esterification, is esterified in heating
Reaction process generates water, and aqueous vapor is discharged after being generated by reaction kettle；After the completion of dehydration, start to carry out depressurization condensation reaction, polycondensation
Ester exchange reaction dealcoholysis is carried out in journey, and excessive dihydric alcohol and a small amount of side reaction product are discharged, obtain acid value AV, hydroxyl value meets
The product of target, the acid value AV specification requirement 0.5 is hereinafter, hydroxyl value specification is set according to molecular weight demand.The polyadipate second
Raw material used in glycol butanediol ester is AA and EG, BG, and raw material used in polyadipate -1,6- hexylene glycol ester is AA and HG, is gathered
Raw material used in phthalic acid neopentyl glycol ester is PA and NPG.
The definition of aforementioned acid value AV is i.e.: acid contained in every gram of sample consumes the quality (mg) for being equivalent to KOH, is represented by
mgKOH/g.With reference to examination criteria ASTM D4662.
Preferably, aforementioned solvent misture is comprising rosin resin or derivatives thereof, terpene resin or derivatives thereof, to change
Kind adhesive initial stage bonding action, further preferred modified rosin resin, the total weight based on the polyurethane hot melt, increasing stick
Resin content is 5-12wt%.
Preferably, the antioxidant is Hinered phenols antioxidant, preferably β (3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Pentaerythritol ester (CHINOX 1010), β (3,5- di-t-butyl -4- hydroxy phenyl) propionic acid octadecyl alcohol ester (CHINOX
1076) in any one or at least two mixture, further preferred CHINOX 1010 be based on the adhesive for polyurethane
Total weight, antioxidant additive amount be 0.1-0.3wt%.
Preferably, aforementioned diisocyanates are MDI ('-diphenylmethane diisocyanate), isocyanic acid in the diisocyanate
The molar ratio of hydroxyl in ester group and polyol ester is 1.6-1.9:1；Total weight based on the adhesive for polyurethane, this is two different
The content of cyanate is 10 to 25wt%.
Preferably, aforementioned catalyst is amine catalyst N,N-Dibenzylamine added with machine Zinc catalysts mixture, different for promoting
The cross-linking reaction of isocyanate group and aqueous vapor after the fast reaction and processing of cyanic acid ester group and hydroxyl.
Preferably, the present invention contains levelling agent, promotes the film that an even uniform is formed in hot melt adhesive film forming procedure,
Adhesive surface tension can be effectively reduced, improve its levelability and uniformity.The permeability of adhesive can be improved, increase attachment
Power.The levelling agent is acrylic acid esters co-polymer macromolecule, preferably MODAFLOW Resin, based on the adhesive for polyurethane
Total weight, levelling agent additive amount are 0.1-0.3wt%.
Specifically, in above mentioned step S3, NCO% is determined using di-n-butylamine titration, detailed process refers to examination criteria
ISO 14896。
A kind of stone plastic floor (SPC) muting pad of the present invention is compound to use reaction type polyurethane hot-melt adhesive, contains by weight percentage
Have: polyol ester 70-80%, diisocyanate 10-25%, solvent misture 5-12%, catalyst 0.02-0.1%, levelling agent
0.10-0.30%, antioxidant 0.1-0.3%, the sum of weight percentage of each component are 100%.
Stone plastic floor (SPC) muting pad above-mentioned is compound to be applied with reaction type polyurethane hot-melt adhesive in production ground decoration material
Material, SPC plate/TPE, SPC plate/EVA, SPC plate/non-woven fabrics.
Compound stone plastic floor (SPC) muting pad of the invention with reaction type polyurethane hot-melt adhesive is one-component hot-melt adhesive, nothing
Need to be solidified using crosslinking agent, instead by molecular resin chain end have response type NCO functional group with it is wet
Gas (water) is reacted to achieve the purpose that crosslinking.In the present invention, with the excessive diisocyanate of 1.6-1.9 times of investment of hydroxyl equivalent
Ester detects the percentage composition NCO% of isocyanate group, by its weight percent during reacting progress at regular intervals
The extent of reaction can be monitored.
Compared with the existing technology, the invention has the beneficial effects that:
(1), adhesive of the invention is single-component polyurethane adhesive, and solid content 100% is free of solvent, is good for the environment
And safety in production, the Compound Machining suitable for the materials such as floor decorative material SPC plate and TPE, EVA, non-woven fabrics.
(2), without matching glue when using, can reduce manually leads to final product quality instability problem with glue, and technical process is simple,
Without pressure maintaining, technical process is simplified, high production efficiency reduces production cost.
(3), the polyurethane hot melt cohesive energy that method of the invention is produced is high, initial solidification speed with higher and
Adhesive strength can prevent compound rear muting pad contraction distortion.It is high to solidify after-tack fusing point, the compound rear floor SPC muting pad is received
Shrinkage is low, and heat resistance is excellent, and dimensional stability is high.Muting pad shrinking percentage can meet the floor SPC receipts less than 2.5 ‰ after compound
Shrinkage testing standard: 80 DEG C, 6 hours standards.Peel strength reaches 10.0N/5cm or more simultaneously.
(4), there is outstanding stability and durability with the compound floor SPC of the hot melt adhesive, there is common ground material
The sound-absorbing effect that can not be compared is applicable to quiet environment (such as indoor house ornamentation, hospital ward, school library, report
The Room, cinema etc.) etc. public places.
In short, the present invention uses polyester polyol (i.e. polyol ester), diisocyanate is basic raw material, auxiliary agent of arranging in pairs or groups,
And make 1.6~1.9:1 of molar ratio of isocyanate group and hydroxyl, stone plastic floor (SPC) is prepared through high temperature polymerization reaction
Muting pad is compound to use reaction type polyurethane hot-melt adhesive.Product of the present invention solid content 100% is free of solvent, which has excellent first
Phase and later period then fastness, solidification after-tack fusing point is high, especially suitable for stone plastic floor (SPC) and mute cushion material be TPE,
The bonding of EVA, non-woven fabrics etc. is compound, and the compound rear floor SPC muting pad shrinking percentage is low, and heat resistance is excellent, and dimensional stability is high.
Detailed description of the invention
Fig. 1 is a kind of compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor (SPC) muting pad of the invention
Flow diagram；
Fig. 2 is a kind of compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor (SPC) muting pad of the invention
The infrared spectrogram of the product of embodiment 1；
Fig. 3 is the infrared spectrogram of the product of the embodiment of the present invention 2；
Fig. 4 is the infrared spectrogram of the product of the embodiment of the present invention 3；
Fig. 5 is prepared using stone plastic floor of the present invention (SPC) muting pad is compound with reaction type polyurethane hot-melt adhesive
The floor SPC.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Stone plastic floor (SPC) muting pad is compound to be hardened with reaction type polyurethane hot-melt adhesive without using crosslinking agent, is taken
And instead of be by molecular resin chain end there is reactive NCO functional group to be reacted with moisture (water) to reach friendship
The purpose of connection.It mainly forms the prepolymer for being end for NCO base, as follows with the reaction mechanism of moisture:
R-NCO+H2O→R-NH2+CO2↑+R’-NCO→R- NH-CO-NH-R’
R’-NH-CO-NH-R”+OCN-R→R-NH-CO- NR’–CO-NH-R”
NCO functional group can first react with the aqueous vapor of air or substrate surface at the beginning generates amido, releases simultaneously
CO2, amido again with other NCO bases the reaction was continued formed have urea functional group structure.Due to still having in urea structure
Active hydrogen, therefore can also make further react with the complete NCO base of unreacted again and generate biuret structure, completion is so-called
Cross-linking reaction.
The floor SPC is a kind of common floor decorative material, and fitting uses two-component cold glue or pressure-sensitive glue laminating more at present,
Two-component glue must carry out before to scale with being bonded after glue again, and it is compound after need through a long time pressure maintaining to can be only achieved foot
Enough fastness, and reaction type polyurethane hot-melt adhesive is not necessarily to pressure maintaining, can reduce manually causes final product quality unstable with glue without matching glue
Determine problem, production process is short, reduces production cost.Pressure sensitive adhesive belongs to one-component solvent-free non-reactive hot melt adhesive, is conducive to ring
It protects and keeps the safety in production, however its defect mainly causes heat resistance and cohesive force insufficient without cross-linking reaction, viscosity is affected by temperature
More apparent, the compound good floor SPC is transported for long-distance under high temperature action and in hot environment through counter in use, pressure sensitive adhesive stickiness drops
It is low to lead to sound-absorbing pad contraction distortion and degumming problem, to influence SPC floor quality.Reaction type polyurethane hot-melt adhesive exploitation can
The present floor SPC muting pad is solved two-component cold glue cost and yield issues are used in combination and improve using pressure sensitive adhesive heat resistance not
The problem of foot promotes the quality of production on the floor SPC, serves multiple.
Raw material illustrates: raw material used in the present invention is self-produced or commercially available.Wherein, polyadipate ethylene glycol butanediol ester
(raw material: AA+EG+BG；Molecular weight: 2000-3000), polyadipate -1,6- hexylene glycol ester (raw material: AA+HG；Molecular weight:
3000-5000), poly- phthalic acid neopentyl glycol ester (raw material: PA+NPG；Molecular weight: 700-1500) it company is voluntarily given birth to by me
Produce manufacture.The manufacturer of diisocyanate (MDI) is Huntsman Corporation, and solvent misture manufacturer is Arizona chemistry,
The manufacturer of catalyst is TMG, and the manufacturer of levelling agent is Qing Te company, and the manufacturer of antioxidant is double bond.
Test equipment and test method
1, examination of infrared spectrum: fourier infrared spectrometer (Fourier Transform Infrared is used
Spectrometer, FTIR), model NICOLET IS5, setting range 4000-650cm-1, to determine the structure of product.
2, determination of moisture: with moisture value contained by karl Fischer formula (Karl-Fischer) moisture teller detection material.
The constituent of your reagent of karl Fischer is iodine, sulfur dioxide, alkali and alcohols equal solvent, reagent quantitative, selectively
It reacts with water, the principle is as follows shown in the chemical formula of face:
I2+SO2+3 Base+ROH+H2O→2 Base。HI+Base·HSO4R
Test process is the mode based on volumetric titrimetry: being put into the dehydrated solvent for being suitable for sample in a beaker, uses
Titrant shifts all moisture from the solvent, then, sample is added, is titrated with titrant, titer (mgH2O/
Ml) be it is pre-determined, the moisture content of sample is determined by titration capacity (ml), uses electrode end point detectable.
3, di-n-butylamine (Dibutylamine) measuring method of NCO%: is dissolved in ethyl acetate (ethyl
Ethanoate), it is allowed to react with NCO, excessive di-n-butylamine is titrated with normal hydrochloric acid liquid (hydrochloric acid), is surveyed
Obtain NCO content in sample, reference standard ISO 14896.
4, the measuring method of film physical property: by hot-melt adhesive membrane cut-parts with electronic tension tester, with rate of extension
200mm/min test, 100%M (modulus), TS (tensile strength), EL (elongation), unit are (Kg/cm2) reference standard ASTM
D-412。
5, softening point, fusing point: using Oven Method by hot-melt adhesive membrane cut-parts, hoist conversion table softening point: is compareed according to film thickness
(every square centimeter of 45 grams of loading) weighs after corresponding weight is clipped in below test piece, test piece is fixed on above baking oven, open plus
Heat, heating rate are 2 DEG C/1min, and record test piece starts the temperature for extending and being broken, respectively its softening point and fusing point.
6, then peel strength test: 23 DEG C of room temperature, 50% ring of relative humidity are placed in the floor SPC of compound good muting pad
Naturally the Bonding strength between two plates is tested after curing 48hr under border, unit is (N/5cm).
7, thermal contraction performance is tested: 23 DEG C of room temperature, 50% environment of relative humidity are placed in the floor SPC of compound good muting pad
After the lower 48hr of curing naturally, 80 DEG C of baking ovens are placed in sampling, observe contraction situation after 6 hours.
Embodiment 1
As shown in Figure 1, to prepare a kind of stone plastic floor (SPC) muting pad compound with reaction type polyurethane hot-melt adhesive by the present invention
Preparation method the following steps are included:
Use two kinds of polyol esters: polyadipate ethylene glycol butanediol ester (molecular weight 2000), poly- phthalic acid are new
Pentadiol ester (molecular weight 1000) puts into above-mentioned two kinds of raw materials into reaction kettle, in addition, putting into antioxidant again, antioxidant adds
Dosage is the 0.1-0.3% of raw material gross weight.
Raw material heating in polymerization reaction kettle is melted and is uniformly mixed, slow heating makes material temperature reach 110-120
DEG C, it vacuumizes and the vacuum degree in reaction kettle is down to 50torr hereinafter, then starting to be dehydrated, nitrogen charging after continuous negative pressure state 1-3h
Reply normal pressure detection material contained by moisture value, if moisture value reach 300ppm hereinafter, if terminate to be dehydrated, if moisture value is higher than
300ppm then returns to negative pressure state and continues to be dehydrated；
Normal pressure is replied after dehydration in reaction kettle, 80-90 DEG C is cooled the temperature to and is passed through nitrogen and maintain reaction kettle micro- just
Pressure, the equivalent of consumption diisocyanate (MDI) needed for being calculated according to polyol ester molecular weight, with the 1.6-1.9 of polyol ester equivalent
Investment excess diisocyanate again, by reaction kettle heating and 100-110 DEG C of maintaining reaction temperature, reaction time 2h reacted
(20-30min) detects the weight percentage NCO% of isocyanate group at regular intervals in journey, when NCO% reaches theoretical value
When following, the sum of the raw material gross weight catalyst of 0.02-0.1% and the levelling agent of 0.1-0.3% are added into reaction kettle, stirring is equal
It is even and reaction kettle is warming up in 110-120 DEG C of negative pressure deaeration and sustained response to reaction kettle bubble-free reaction terminates, it is produced
Product appearance is colorless and transparent glutinous thick liquid.Wherein, isocyanate group and hydroxy equivalent proportion are 1.65:1, and diisocyanate is
'-diphenylmethane diisocyanate (MDI), antioxidant be Hinered phenols antioxidant CHINOX 1010, catalyst be amine catalyst (such as
Amine catalyst N,N-Dibenzylamine DMDEE) add organic zinc class mixture, levelling agent is acrylic acid esters co-polymer macromolecule
MODAFLOW Resin.The present embodiment product basic recipe is following (weight ratio):
1 embodiment of table, 1 product basic recipe
It is finally tested for the property, infrared spectrum analysis as shown in Figure 2, performance test is shown in Table 4.
The present embodiment product flow leveling is good, and initial stage is then and later period Bonding strength is high, be suitable for the floor SPC and TPE,
Non-woven fabrics is then.
Stone plastic floor (SPC) muting pad is compound to suggest processing method on the floor reaction type polyurethane hot-melt adhesive application SPC
It is as follows:
1. melten gel: using press disc type glue-smelting machine, melt adhesive temperature is arranged 110-140 DEG C.
2. gluing compound: after using muting pad laminating machine, solid gum to heat fusing in glue-smelting machine, gluing work by roller coating
Skill is coated on adhesive uniformly on SPC, 110-130 DEG C of upper glue roller set temperature, and spread controls between 35-50g/m2
(adjusting spread according to the flatness of SPC commissure), then composite silencing pad (TPE, EVA, the non-woven fabrics) on laminating machine.
3. placing room temperature maturation after compound.
The floor SPC is countries in the world today using a kind of extensive new terrestrial ornament materials, and development prospect is boundless.
This patent provides that a kind of novel stone plastic floor (SPC) muting pad is compound with reaction type polyurethane hot-melt adhesive formula and to prepare the tree
The method of rouge must make floor decorative material reach better quality water product.
As shown in Figure 5 it is compound after the floor SPC.It is marked in description of the invention attached drawing as follows:
1-SPC board finish；2-SPC plate reinforced structure layer；3- adhesive layer；4- muting pad (EVA, TPE).
Embodiment 2
The present embodiment is identical as 1 processing procedure of embodiment, and difference place is: the present embodiment uses three kinds of polyalcohols, comprising poly-
Adipic acid hexylene glycol ester (molecular weight 3700), polyadipate ethylene glycol butanediol ester (molecular weight 2000), poly- O-phthalic
Sour neopentyl glycol ester (molecular weight 1000), weight ratio is set as 300:400:350.Formula is added compared to embodiment 1 into height
Molecular weight high crystalline polyadipate hexylene glycol ester, shortens the open hour of product of the present invention, further promotes initial cure speed
Degree, isocyanate group and hydroxy equivalent proportion are 1.65:1 in formula, and diisocyanate is '-diphenylmethane diisocyanate
(MDI), solvent misture is added and in formula and increases initial adhesion force, to increase the attachment fastness to various substrates, antioxidant be by
Phenolic antioxidant CHINOX 1010 is hindered, catalyst is amine catalyst (such as amine catalyst N,N-Dibenzylamine DMDEE) plus organic zinc
Class mixture, levelling agent are acrylic acid esters co-polymer macromolecule MODAFLOW Resin.
The present embodiment product basic recipe is following (weight ratio):
2 embodiment of table, 2 product basic recipe
It is finally tested for the property, infrared spectrum analysis as shown in Figure 3, performance test is shown in Table 4.
The present embodiment product is compared with 1 product of embodiment, increases high crystalline polyalcohol and solvent misture in formula, is promoted
Initial cure speed and initial stage adhesion prevent the just compound good floor SPC from following layer displacement, and applicable base materials model occurs
It encloses more extensively, is suitable for the floor SPC and TPE, EVA, non-woven fabrics then.
Embodiment 3
The present embodiment is identical as 1 processing procedure of embodiment, and the present embodiment polyol ester uses polyadipate 1,6- hexylene glycol ester
(molecular weight 3700), poly- phthalic acid neopentyl glycol ester (molecular weight 1000), weight ratio is set as 800:250.Formula
Design is with high crystalline high molecular weight adipic acid 1, based on 6- hexylene glycol ester, further shortens the glue curing time, this product can
It adapts to summer high temperature environment to remain to maintain faster crystallization rate, and promotes the adding proportion of solvent misture in formula, increase just
Beginning adhesive force prevents summer high temperature processing from generating substrate displacement cissing phenomenon.Isocyanate group and hydroxy equivalent proportion in formula
For 1.8:1, isocyanates is '-diphenylmethane diisocyanate (MDI), and antioxidant is Hinered phenols antioxidant CHINOX 1010,
Catalyst is amine catalyst (such as amine catalyst N,N-Dibenzylamine DMDEE) plus organic zinc class mixture, and levelling agent is acrylic acid
Lipin polymer macromolecule MODAFLOW Resin.
The present embodiment product basic recipe is following (weight ratio):
3 embodiment of table, 3 product basic recipe
| Formula | Weight | Content (WT%) |
| Polyadipate hexylene glycol ester | 800 | 54.6 |
| Poly- phthalic acid neopentyl glycol ester | 250 | 17.06 |
| '-diphenylmethane diisocyanate (MDI) | 209.8 | 14.32 |
| Antioxidant | 2.9 | 0.2 |
| Catalyst | 0.42 | 0.03 |
| Levelling agent | 2.2 | 0.15 |
| Solvent misture | 200 | 13.65 |
It is finally tested for the property, infrared spectrum analysis as shown in Figure 4, performance test is shown in Table 4.
The present embodiment product has rapid crystallization performance, is suitable for summer high temperature environment processing, prevents summer high temperature from processing
It generates substrate and is displaced cissing phenomenon.And solvent misture ratio is high, product applicable base materials range is wider, be suitable for the floor SPC with
TPE, EVA, non-woven fabrics, cork are then.
Performance evaluation
It is the infrared structure spectrogram of the product of embodiment 1-3 shown in Fig. 2,3,4, by spectrogram as it can be seen that this polyurethane-hot melt
Adhesive finished product, 1719-1725cm-1There is an apparent sharp peak at place, has esters principal character peak.2260-2270cm-1Place
There is an apparent sharp peak, active NCO characteristic peak is anti-by carrying out with reactive NCO functional group and moisture (water)
It should achieve the purpose that crosslinking.Embodiment 2-3 is in 1166cm-1There is obvious vibration peak at wave number, is solvent misture characteristic peak, to
Composite base material initial stage adhesion.740cm-1There is obvious vibration peak at wave number, there is aromatic polyester polyol principal character peak, mention
Adhesive force of the height to difficult then substrate (low polarity).
Table 4 is the Physical Property Analysis data statistic of product obtained by embodiment 1-3.By table 4 as it can be seen that anti-tensile is strong after maturation
It spends up to 300kgf/cm2More than, the good then fastness in the floor SPC is assigned, up to 10N/5cm or more, softening point range exists
120 DEG C or more, show that product has
Excellent heat resistance, 80 DEG C, observation contraction situation is qualified within 6 hours.
Remarks: the compound EVA substrate in the floor test material SPC
4 embodiment 1-3 the performance test results of table
In conclusion it with reaction type polyurethane hot-melt adhesive is single group that a kind of stone plastic floor (SPC) sound-absorbing pad of the present invention is compound
Part adhesive for polyurethane, the solid content of product are 100%, are good for the environment and keep the safety in production, are suitable for floor decorative material SPC
The Compound Machining of the materials such as plate and TPE, EVA, non-woven fabrics.Tensile strength is high after product solidification of the invention, and softening fusing point is high, fits
Wide with base material range, the compound rear floor SPC muting pad shrinking percentage is low, and heat resistance is excellent, and dimensional stability is high, can solve commercially available double
The temperature tolerance problem of component cold glue processing problems and pressure sensitive adhesive.The compound floor SPC of this project hot melt adhesive has outstanding stabilization
Property and durability, the sound-absorbing effect for having common ground material that can not compare, the floor SPC both solved solid wooden floor board dampness deformation
Mildew and rot problem, and solve the Formaldehyde of other finishing materials.Its alternative color pattern is numerous, is suitable for indoor family
Dress, hotel, hospital, the public places such as market.The floor SPC is that countries in the world today uses a kind of extensive new terrestrial decoration material
Material, very popular in European & American Market and Asia-Pacific market, also very universal in China, application development prospect is boundless.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the above embodiments do not limit the invention in any form, all obtained by the way of equivalent substitution or equivalent transformation
Technical solution is fallen within the scope of protection of the present invention.
Claims (10)
1. a kind of compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad, which is characterized in that this method
It the use of polyol ester, diisocyanate is basic raw material, auxiliary agent of arranging in pairs or groups, and make isocyanate group and the molar ratio of hydroxyl 1.6
The compound reaction type polyurethane heat of stone plastic floor muting pad that solid content is 100% is prepared through high temperature polymerization reaction in~1.9:1
Melten gel.
2. a kind of compound preparation side with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 1
Method, which comprises the steps of:
S1, it will be put into polymerization stirred autoclave after polyol ester, solvent misture, antioxidant metering, wherein the polyalcohol
Ester is polyadipate ethylene glycol butanediol ester, polyadipate -1,6-HD ester, one kind of poly- phthalic acid neopentyl glycol ester
Or it is several；The antioxidant is Hinered phenols antioxidant, and the total weight based on the polyurethane hot melt, antioxidant additive amount is
0.1-0.3 wt%；The solvent misture be rosin resin, rosin resin derivative, terpene resin, terpene resin derivative one
Kind or several, the total weight based on the polyurethane hot melt, solvent misture additive amount are 5-12 wt%；
S2, the raw material heating polymerizeing in stirred autoclave is melted and is uniformly mixed, slow heating makes material temperature reach 110-
It 120 DEG C, vacuumizes and the vacuum degree in reaction kettle is down to 50torr hereinafter, then starting to be dehydrated, after continuous negative pressure state 1-3h
Nitrogen charging replys normal pressure with moisture value contained by karl Fischer formula (Karl-Fischer) moisture teller detection material, if moisture value
Reach 300ppm (mg/kg) hereinafter, then terminating to be dehydrated, if moisture value is higher than 300ppm, returns to negative pressure state and continue to be dehydrated；
Normal pressure is replied after S3, dehydration in reaction kettle, 80-90 DEG C is cooled the temperature to and is passed through nitrogen and maintain reaction kettle micro- just
Pressure, the equivalent of diisocyanate needed for calculating according to polyol ester molecular weight, the diisocyanate are two isocyanide of diphenyl-methane
Acid esters puts into excess diisocyanate with 1.6-1.9 times of polyol ester equivalent, by reaction kettle heating and maintaining reaction temperature
100-110 DEG C, the reaction time is not less than 2h, detects the weight percentage of isocyanate group in reaction process at regular intervals
The total weight 0.02- based on the polyurethane hot melt is added into reaction kettle when NCO% reaches theoretical value or less by NCO%
0.1% catalyst and the levelling agent of 0.10-0.30% stir evenly and reaction kettle are warming up to 110-120 DEG C of negative pressure deaeration and is held
Continuous reaction to bubble-free reaction in reaction kettle terminates, and product appearance is colourless to stick thick liquid to yellow；The catalyst is amine
Add organic zinc class mixture, levelling agent is acrylic acid esters co-polymer macromolecule；
S4, after completion of the reaction, obtains colourless to the sticky shape liquid product of yellow.
3. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 2,
Be characterized in that, in the step S1, polyadipate ethylene glycol butanediol ester molecular weight be 2000-3000, polyadipate 1,6- oneself
The molecular weight of diol ester is 3000-5000, and poly- phthalic acid neopentyl glycol ester molecular weight is 700-1500；Based on the polyurethane
The total weight of adhesive, the content of the polyol ester are 70 to 80 wt%.
4. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 1,
It is characterized in that, the diisocyanate is MDI '-diphenylmethane diisocyanate, isocyanate group and polyalcohol in diisocyanate
The molar ratio of hydroxyl in ester is 1.6-1.9:1；Total weight based on the adhesive for polyurethane, the content of the diisocyanate
For 10 to 25 wt%.
5. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 1,
It is characterized in that, the auxiliary agent includes solvent misture, antioxidant, catalyst, levelling agent.
6. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 5,
It is characterized in that, the solvent misture is one kind of rosin resin, rosin resin derivative, terpene resin, terpene resin derivative
Or it is several, to improve adhesive initial stage bonding action, further preferred modified rosin resin, based on the polyurethane hot melt
Total weight, solvent misture additive amount are 5-12 wt%.
7. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 5,
It is characterized in that, the antioxidant is Hinered phenols antioxidant, is β (3,5- di-tert-butyl-hydroxy phenyl) propionic acid pentaerythrite
Appointing in ester (CHINOX 1010), β (3,5- di-tert-butyl-hydroxy phenyl) propionic acid octadecyl alcohol ester (CHINOX 1076)
It anticipates a kind of or at least two mixtures, further preferred CHINOX 1010；Total weight based on the adhesive for polyurethane
Meter, antioxidant additive amount are 0.1-0.3 wt%.
8. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 5,
It is characterized in that, the catalyst is amine catalyst N,N-Dibenzylamine added with machine Zinc catalysts mixture, for promoting isocyanates
The cross-linking reaction of isocyanate group and aqueous vapor after the fast reaction and processing of base and hydroxyl.
9. the compound preparation method with reaction type polyurethane hot-melt adhesive of stone plastic floor muting pad according to claim 5,
It is characterized in that, the levelling agent is acrylic acid esters co-polymer macromolecule, and preferably MODAFLOW Resin is based on the polyurethane
The total weight of adhesive, levelling agent additive amount are 0.1-0.3 wt%.
10. the compound poly- ammonia of response type of the stone plastic floor muting pad that preparation method described in -9 is prepared according to claim 1
Ester hot melt adhesive, which is characterized in that contain by weight percentage: polyol ester 70-80%, diisocyanate 10-25%, increasing stick tree
Rouge 5-12%, catalyst 0.02-0.1 %, levelling agent 0.10-0.30%, antioxidant 0.1-0.3%, the sum of weight percentage of each component are
100% 。
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| CN201811172342.6A CN109456726A (en) | 2018-10-09 | 2018-10-09 | A kind of stone plastic floor muting pad is compound to use reaction type polyurethane hot-melt adhesive and preparation method |
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| CN114607114A (en) * | 2022-03-09 | 2022-06-10 | 常州市贝美家居科技有限公司 | Composite floor and preparation method thereof |
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Application publication date: 20190312 |