WO2024046422A1 - Method for additive manufacturing of wearable consumer goods - Google Patents

Abstract

Disclosed in the present invention is a method for additive manufacturing of wearable consumer goods, comprising: using an organic silicon composition for 3D printing to prepare organic silicon sheets, performing splicing and post-treatment on the organic silicon sheets, and then preparing the organic silicon sheets and textile into wearable consumer goods; or using an organic silicon composition on a textile base material for 3D printing to prepare a composite sheet, performing post-treatment, and then preparing the composite sheet into wearable consumer goods. Also disclosed are an organic silicon fabric, and wearable consumer goods made by means of the method in the present invention or by using the organic silicon sheets or composite sheet in the present invention.

Description

Methods for additive manufacturing of wearable consumer products Technical field

The present invention relates to the application of 3D printable silicone compositions in the manufacture of wearable consumer products, such as clothing, shoes, hats, bags and accessories.

Background technique

In recent years, 3D printing technology (or additive manufacturing technology) has developed rapidly. The rapid manufacturing of parts can be achieved through the principle of layer-by-layer superposition. It has the characteristics of reducing product development cycles, improving material utilization, and customizing complex special-shaped structural parts. 3D printing encompasses different technologies whose common feature is the automated additive accumulation of layers of shaped parts. Addition cross-linked silicone compositions have been used in 3D printing methods to produce three-dimensional elastomeric silicone articles or parts. Such silicone compositions are disclosed, for example, in CN104559196B, CN105238064A, CN105637035A and CN107141426A. The 3D printing technologies that can be used for silicone sheets mainly include extrusion 3D printing technology and light-curing molding technology.

Among the disclosed patents related to silicone 3D printing, they basically focus on the development of silicone printing materials, printing equipment and processes. Combining the excellent performance of silicone sheets with 3D printing technology, it should have unique application advantages in areas such as clothing and accessories. However, the application of existing 3D printing materials on the market in clothing and other fields currently has the following problems:

(1) The material is hard, and there are deviations in properties such as spreadability and tear resistance;

(2) Due to limited material performance, the structural design is too exaggerated and can only be used for display and cannot be truly used in consumer fields such as daily wearables;

(3) The design principles and printing process requirements of 3D printing technology for corresponding materials are not applicable;

(4) 3D printing technology commonly uses the wire extrusion printing process of thermoplastic materials or silicone-like sheets or the thermosensitive resin light-curing printing process, which cannot be directly used for 3D printing of silicone sheets;

(5) Due to printing size limitations, large-size clothing or accessories also need to solve technical problems such as splicing and surface post-processing after printing.

Due to the above reasons, there are no solutions for silicone 3D printing in the fields related to wearable consumer products.

Contents of the invention

One object of the present invention is to provide a method for additive manufacturing of wearable consumer products, such as clothing, shoes, hats, bags, accessories, etc. The silicone sheet produced by this method has suitable mechanical properties and is suitable for making wearable consumer products through splicing, cutting, sewing, etc.

Another object of the present invention is to provide 3D printed silicone sheets or composite sheets. The silicone sheet or composite sheet is suitable for fields related to wearable consumer goods and is expected to truly promote the large-scale application of this technology in the field of wearable consumer goods.

Another object of the present invention is to provide silicone fabrics suitable for manufacturing wearable consumer products.

Yet another object of the present invention is to provide wearable consumer products containing silicone.

The silicone composition of the present invention can achieve low modulus, high elasticity, and good weather resistance and ultraviolet resistance. The silicone sheet produced by the silicone composition through different 3D printing processes can achieve suitable mechanical properties and meet the requirements of wearable consumer products in terms of feel, softness, touch, personalized design and printing accuracy. The silicone sheet can be made into wearable consumer products that meet a variety of needs, such as clothing, shoes, hats, bags, accessories, etc.

Description of drawings

Figure 1 is an example of a silicone sheet of the present invention.

Figure 2 is an example of the silicone fabric of the present invention, which is spliced by the silicone sheets of the present invention.

Figure 3 is a partial illustration of a wearable consumer product of the present invention, which is spliced by the silicone fabric of the present invention and traditional textiles.

Detailed ways

A first aspect of the invention relates to a method for additive manufacturing of a wearable consumer product, said method comprising the steps of:

1) 3D print the silicone composition into silicone sheets;

2) Use the silicone sheet to manufacture wearable consumer products.

The method for additive manufacturing of wearable consumer products of the present invention may also include the following steps:

1) 3D print the silicone composition into a composite sheet on the wearable fabric substrate;

2) Use the composite sheet to manufacture wearable consumer products.

3D printing content

3D printing is often associated with a number of related technologies for manufacturing physical objects from computer-generated (such as computer-aided design (CAD)) data sources.

The contents of this article are generally incorporated into ASTM Designation F2792-12a, "Standard Terminology for Additive Manufacturing Technologies Under this ASTM standard".

"3D printer" is defined as "a machine for 3D printing" and "3D printing" is defined as "the use of a print head, nozzle, or other printer technology to create an object by depositing material."

“Additive Manufacturing (AM)” is defined as “the process of joining materials from 3D modal data to create an object, typically layer by layer, as opposed to subtractive manufacturing techniques.” Synonyms related to and covered by 3D printing include additive manufacturing, additive processes, additive technologies, additive layer manufacturing, layer manufacturing and freeform manufacturing. Additive manufacturing (AM) can also be called rapid prototyping (RP). As used herein, "3D printing" is often interchangeable with "additive manufacturing" and vice versa.

"Printing" is defined as depositing a material (here, a silicone composition) using a printhead, nozzle, or other printer technology.

As used herein, "3D or three-dimensional article, object or component" refers to an article, object or component obtained by additive manufacturing or 3D printing as disclosed above.

Typically, all 3D printing processes have a common starting point, which is a computer-generated data source or program that describes the object. Computer-generated data sources or programs can be based on real or virtual objects. For example, real objects can be scanned using a 3D scanner, and the scanned data can be used to make a computer-generated data source or program. Alternatively, computer-generated data sources or programs can be designed from scratch.

Computer-generated data sources or programs are typically converted to the Standard Mosaic Language (STL) file format; but other file formats may or may be additionally used. This file is typically read into 3D printing software, which takes the file and optional user input to divide it into hundreds, thousands, or even millions of "slices." 3D printing software typically outputs machine instructions, which can be in the form of G-code, which is read by the 3D printer to build each slice. The machine instructions are transmitted to the 3D printer, which then builds the object layer by layer based on this slice information in the form of machine instructions. The thickness of these slices can vary.

An extrusion 3D printer is a type of 3D printer in which material is extruded through a nozzle, syringe, or orifice during the additive manufacturing process. Material extrusion is typically performed by extruding material through a nozzle, syringe, or orifice to print a cross-section of the object, which can be repeated for each subsequent layer. The extruded material bonds to the layer beneath it while the material solidifies.

In a preferred embodiment, a method for additively manufacturing three-dimensional silicone elastomeric articles uses an extrusion 3D printer. The silicone composition is extruded through a nozzle. The nozzle can be heated to help dispense the addition crosslinkable organic Silicon composition.

The addition-crosslinking silicone composition dispensed through nozzles can be supplied from a cartridge-like system. The cartridge may include one or more nozzles with associated one or more fluid reservoirs. A coaxial twin-box system with a static mixer and only one nozzle is also available. The pressure will be adapted to the fluid to be dispensed, the associated average nozzle diameter and the print speed.

Due to the high shear rates that occur during nozzle extrusion, the viscosity of the addition crosslinkable silicone composition is greatly reduced, and therefore fine layers can be printed.

The nozzle and/or build platform moves in the X-Y (horizontal plane) to complete the cross-section of the object before moving in the Z-axis (vertical) plane once a layer is completed. The nozzle has high XYZ movement accuracy of approximately 10μm. After each layer is printed on the X,Y working plane, the nozzle is only moved far enough in the Z direction to apply the next layer in the X,Y working position. In this way, objects that become 3D artifacts are built one layer at a time from bottom to top.

As disclosed above, the distance between the nozzle and the front layer is an important parameter to ensure good shape. Preferably, it should be between 60% and 150% of the average diameter of the nozzle, preferably between 80% and 120%.

Advantageously, the printing speed is 1-50 mm/s, preferably 5-30 mm/s, to obtain the best compromise between good accuracy and manufacturing speed.

"Material jetting" is defined as "an additive manufacturing process in which droplets of build material are selectively deposited." With the aid of a print head, the material is applied discontinuously (jetting) in the form of individual droplets at the desired position on the working plane. Apparatus and methods for the stepwise production of 3D structures using a printhead arrangement containing at least one, preferably 2-200 printhead nozzles, allow for the site-selective application of multiple materials where appropriate. Applying materials via inkjet printing places specific requirements on the viscosity of the material.

In a material jet printer, one or more reservoirs are subjected to pressure and connected to the metering nozzle via metering lines. There may be a device upstream or downstream of the reservoir capable of uniformly mixing the multi-component addition crosslinkable silicone composition and/or discharging dissolved gases. There may be one or more injection devices operating independently of each other to construct elastomeric articles from different addition-crosslinking silicone compositions, or in the case of more complex structures, to allow for the construction of elastomeric articles from silicone elastomers and other plastics. composite parts.

Due to the high shear rates occurring in the metering valve during injection metering, the viscosity of this addition-crosslinking silicone composition is greatly reduced and thus allows the injection metering of very fine microdroplets. After the droplet is deposited on the substrate, its shear rate suddenly decreases and therefore its viscosity rises again. As a result, the deposited droplets quickly become highly viscous again and allow shape-accurate construction of three-dimensional structures.

Individual metering nozzles can be precisely positioned in the x, y, and z directions to allow for precise spot deposition of silicone rubber droplets onto the substrate or, during subsequent formation of the molded part, onto surfaces that have already been placed and optionally On the crosslinked addition crosslinkable silicone rubber composition.

Typically, 3D printers use dispensers, such as nozzles or printheads, for printing specific curable silicone compositions. Optionally, the dispenser can be heated before, during and after dispensing the silicone composition. More than one allocator can be used, each with independently selected capabilities.

In one embodiment, this method may use support materials to construct the object. If support materials or rafts are used to print an object, they are usually removed after the printing process is completed, leaving the finished object.

Another type is 3D printing technology based on photopolymerization. They start with a liquid material and either locally deposit and solidify the material or selectively solidify it from the liquid material. Examples of such technologies are UV stereolithography (SLA), UV digital light processing (DLP), UV extrusion and inkjet deposition. Among them, UV stereolithography (SLA) uses a laser beam scanner system that usually moves in the X-Y (horizontal) plane. Motors guided by information from the generated data source drive image send a laser beam to the surface. In UV digital light processing (DLP), the 3D model is sent to a printer, where the liquid polymer in a container is exposed to the light of a DLP projector under safe lighting conditions. A DLP projector displays an image of a 3D model on liquid polymer. The DLP projector can be installed under a window which can be made of a transparent elastic film, where the UV rays from the DLP projector shine in. In UV extrusion and inkjet deposition processes, material is extruded through a nozzle across a cross-section of the printed object, which can be repeated for each layer. An energy source can be attached directly to the nozzle, allowing it to solidify immediately after extrusion or can be separate from the nozzle to delay solidification. The nozzle or build platform typically moves in the Z-axis (vertical) plane to the previous X-Y (horizontal) plane after each layer is completed. This UV curing can be performed immediately after deposition, or the plate is moved under UV light to create a delay between deposition and UV curing. Support materials can be used to avoid extruding airborne material from the filaments.

Some post-processing can be used to improve the processing quality of the printed surface.

Post-processing options

Optionally, the resulting articles can be subjected to different post-treatment regimens. In one embodiment, the method further includes the step of heating the silicone sheet or composite sheet. Heat can be used to accelerate curing. In another embodiment, the method further includes the step of further irradiating the silicone sheet or composite sheet. Further irradiation can be used to accelerate curing. In another embodiment, the method further includes the two steps of heating and irradiating the silicone sheet or composite sheet.

Optionally, post-processing steps can greatly improve the surface quality of the printed article. Sanding is a common way to reduce or eliminate distinct layers on a model. Spraying or coating the surface of the elastomeric article with a heat or UV curable silicone composition (eg, an RTV or LSR silicone composition) can be used to obtain a suitably smooth surface appearance.

Surface treatment can also be performed with lasers, or the final elastomeric article can be sterilized by heating the object at >100°C or in a UV oven.

Silicone composition

According to the different requirements of the 3D printing process, different types of silicone sheets can be selected, such as addition type, condensation type, light-curing type, etc.

Specifically, the addition-type silicone composition of the present invention contains the following components in weight ratio:

The photocurable silicone composition of the present invention contains the following components in weight ratio:

In addition, another silicone composition can also be used in the extrusion 3D printing process to achieve the effects of the present invention. The silicone composition can be cured by condensation polymerization, that is, a reactive polysiloxane containing condensable or hydrolyzable or hydroxyl groups and an optional curing agent are cured under the action of an optional organic tin or organic titanium catalyst.

An exemplary polycondensation-curable silicone base composition includes:

(a) at least one linear reactive polysiloxane having at least two condensable groups or hydrolyzable groups other than OH at each chain end, or having only hydroxyl groups,

(b) optionally at least one linear non-reactive polysiloxane without condensable or hydrolyzable groups or hydroxyl groups,

(c) optionally at least one cross-linking agent,

(d) Reinforcement filler, which can be white carbon black, silicone resin, calcium carbonate, etc.

(e)Thixotropic agent

(f) Optional other additives, such as pigments, etc.

In linear reactive polysiloxanes with at least two condensable groups or hydrolyzable groups other than OH at each chain end, or only hydroxyl groups, the condensable groups include amino groups, amide groups, Aminooxy, ketiminoxy, iminooxy, alkenyloxy, alkoxy, alkoxy-alkenoxy, acyloxy and phosphate groups, and the condensable groups include hydrogen atoms and halogen atoms, and they can be anywhere along the polysiloxane backbone, that is, at both ends, in the middle, or both ends and the middle.

Each component of the addition silicone composition is described in detail below.

(A) Vinyl-containing organopolysiloxane

The vinyl-containing organopolysiloxane in the silicone composition of the present invention may be an organopolysiloxane containing at least two C ₂ -C ₆ alkenyl groups connected to silicon atoms per molecule, which includes:

(i) At least two siloxane units (A.1), which may be the same or different and have the following formula:

in:

·a=1 or 2, b=0, 1 or 2, and a+b=1, 2 or 3;

The symbol W may identically or differently represent linear or branched C ₂ -C ₆ alkenyl, and

·The symbol Z may identically or differently represent a monovalent linear, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms such as fluorine, chlorine and bromine atoms and/or substituted by one or more aryl groups such as phenyl, and even more preferably selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl, and

(ii) optionally at least one siloxane unit having the formula:

in:

·c=0, 1, 2 or 3,

·The symbol Z1 may identically or differently represent a monovalent linear, containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, Branched or cyclic alkyl groups, which may be unsubstituted or substituted by one or more halogen atoms such as fluorine, chlorine and bromine atoms and/or by one or more aryl groups such as phenyl, and even more preferably Selected from methyl, ethyl, propyl, and 3,3,3-trifluoropropyl.

Advantageously, Z and Z1 are selected from methyl, ethyl and propyl, and W is selected from the following groups: vinyl, propenyl, 3-butenyl, 5-hexenyl, 9-decenyl, 10 - Undecenyl, 5,9-decadienyl and 6,11-dodecenyl, and preferably W is vinyl.

In a preferred embodiment, in formula (A.1) a=1 and a+b=2 or 3 and in formula (A.2) c=2 or 3.

These organopolysiloxanes can have linear, branched or cyclic structures.

When they are linear polymers, they are mainly formed from siloxane units "D" and siloxane units "M" selected from the group consisting of siloxane units W ₂ SiO _2/2 , WZSiO _2/2 and Z ¹ ₂ SiO _2/2 , and the siloxane unit “M” is selected from the group consisting of siloxane units W ₃ SiO _1/2 , WZ ₂ SiO _1/2 , W ₂ ZSiO _1/2 and Z ¹ ₃ SiO _1/2 . The symbols W, Z and Z1 are as described above.

As examples of terminal units “M” there may be mentioned trimethylsiloxy, dimethylvinylsiloxy or dimethylhexenylsiloxy.

As examples of units "D" there may be mentioned dimethylsiloxy, methylvinylsiloxy, methylbutenylsiloxy, methylhexenylsiloxy, methyl Decenylsiloxy or methyldecadienylsiloxy.

The organopolysiloxane may be an oil having a dynamic viscosity of about 1-10,000,000 mPa·s at 25°C, typically about 200-1,000,000 mPa·s at 25°C.

The viscosity considered in this description corresponds to the "Newtonian" dynamic viscosity at 25° C., i.e. at sufficiently low shear velocity gradients that the measured viscosity is independent of the velocity gradient using a Brookfield viscometer in a manner known per se Measured dynamic viscosity.

When they are cyclic organopolysiloxanes, they are formed from siloxane units "D" having the formula: W ₂ SiO _2/2 , Z ¹ ₂ SiO _2/2 or WZSiO _2/2 , which can be It is dialkylsiloxy, alkylvinylsiloxy or alkylsiloxy type. Examples of such siloxane units have been mentioned above. The cyclic organopolysiloxane has a viscosity of about 1 to 5,000 m Pa·s at 25°C.

In a preferred embodiment, component (A) may be a combination of organopolysiloxanes of different viscosities.

In a preferred embodiment, component (A) may be a vinyl-containing linear organopolysiloxane (eg, vinyl-terminated polydimethylsiloxane) and a vinyl-containing organopolysiloxane A combination of resins.

The vinyl-containing organopolysiloxane resin includes:

a) At least two different siloxane units, which are selected from the group consisting of siloxane unit M represented by formula R ₃ SiO _1/2 , siloxane unit D represented by formula R ₂ SiO _2/2 , and formula RSiO _3/2 siloxane units T represented by and siloxane units Q represented by the formula SiO _4/2 , where R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and

b) Provided that at least one of these siloxane units is a siloxane unit T or Q, and at least one of the siloxane units M, D and T contains an alkenyl group.

Therefore, according to a preferred embodiment, the vinyl-containing organopolysiloxane resin may be selected from the following group:

- Organopolysiloxane resin of formula MT ^Vi Q, which basically consists of the following units:

(a) Trivalent siloxane unit T ^Vi of the formula R'SiO _3/2 ;

(b) monovalent siloxane units M of formula R ₃ SiO _1/2 , and

(c) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

- Organopolysiloxane resin of formula MD ^Vi Q, which basically consists of the following units:

(a) Divalent siloxane unit D ^Vi of the formula RR'SiO _2/2 ;

(b) monovalent siloxane units M of formula R ₃ SiO _1/2 , and

(c) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

- Organopolysiloxane resin of formula MDD ^Vi Q, which basically consists of the following units:

(a) Divalent siloxane unit D ^Vi of the formula RR'SiO _2/2 ;

(b) Divalent siloxane unit D of the formula R ₂ SiO _1/2 ,

(c) monovalent siloxane units M of formula R ₃ SiO _1/2 , and

(d) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

- Organopolysiloxane resin of formula M ^Vi Q, which basically consists of the following units:

(a) monovalent siloxane units M ^Vi of the formula R'R ₂ SiO _1/2 , and

(b) tetravalent siloxane unit Q of the formula SiO _4/2 , and

- Organopolysiloxane resin of formula M ^Vi T ^Vi Q, which basically consists of the following units:

(a) Monovalent siloxane unit M ^Vi of the formula R'R ₂ SiO _1/2 ,

(b) trivalent siloxane units T ^Vi of the formula R'SiO _3/2 , and

(c) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

in

R represents a monovalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12, more preferably 1 to 8 carbon atoms, and

R' represents an alkenyl group, preferably an alkenyl group having 2 to 12, more preferably 2 to 6 carbon atoms, particularly preferably ethylene or allyl, most preferably vinyl.

In a further preferred embodiment, the vinyl-containing organopolysiloxane resin may be an organopolysiloxane resin of formula MD ^Vi Q, which essentially consists of the following units:

(a) divalent siloxane unit D ^Vi of the formula RR'SiO _2/2 ;

(b) monovalent siloxane units M of formula R ₃ SiO _1/2 , and

(c) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

where R and R' are as defined above.

Advantageously, the weight average molecular weight of the vinyl-containing organopolysiloxane resin is in the range of 200 to 50,000, preferably in the range of 500 to 30,000. Here, the weight average molecular weight can be converted using gel permeation chromatography using polystyrene as a standard.

In the silicone composition according to the present invention, if a combination of at least one vinyl-containing linear organopolysiloxane and at least one vinyl-containing organopolysiloxane resin is used as component (A), Then in component (A), based on the total weight of the vinyl-containing linear organopolysiloxane and the vinyl-containing organopolysiloxane resin being 1, the vinyl-containing organopolysiloxane resin accounts for The ratio is >0 and ≤0.6, preferably 0.001 to 0.4, more preferably 0.01 to 0.3, even more preferably 0.01 to 0.2.

(B) Silicon-hydrogen bond-containing organopolysiloxane

According to a preferred embodiment, the silicon-containing hydrogen-bonded organopolysiloxane compound is an organopolysiloxane containing at least two hydrogen atoms bonded to the same or different silicon atoms per molecule, and preferably each molecule contains At least three hydrogen atoms bonded directly to the same or different silicon atoms.

Advantageously, the silicon-hydrogen bond-containing organopolysiloxane is an organopolysiloxane, which includes:

(i) At least two siloxane units of the formula and preferably at least three siloxane units of the formula:

in:

·d=1 or 2, e=0, 1 or 2, and d+e=1, 2 or 3;

·The symbol Z3 may identically or differently represent a monovalent linear, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms such as fluorine, chlorine and bromine atoms and/or substituted by one or more aryl groups such as phenyl, and even more preferably selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl, and

(ii) optionally at least one siloxane unit of the formula:

in:

·c=0, 1, 2 or 3;

·The symbol Z2 may identically or differently represent a monovalent linear, branched or cyclic alkyl group containing 1 to 30 carbon atoms, preferably 1 to 8 carbon atoms, which may be unsubstituted or substituted by one or more halogen atoms Such as fluorine, chlorine and bromine atoms and/or substituted by one or more aryl groups such as phenyl, and even more preferably selected from methyl, ethyl, propyl, 3,3,3-trifluoropropyl.

The silicon hydrogen bond-containing organopolysiloxane compound may be formed only of the siloxane group unit of formula (B.1) or may also include the unit of formula (B.2). They can have linear, branched or cyclic structures.

Examples of siloxane-based units of formula (B.1) are in particular the following units: H(CH ₃ ) ₂ SiO _1/2 and HCH ₃ SiO _2/2 .

When they are linear polymers, they are mainly formed from:

• Selected from siloxane units "D" having the formula Z ² ₂ SiO _2/2 or Z ³ HSiO _2/2 units, and

• Selected from siloxane units "M" having the formula Z ² ₃ SiO _1/2 or Z ³ ₂ HSiO _1/2 units.

These linear organopolysiloxanes may have dynamics of about 1-1,000,000 mPa·s at 25°C, typically about 10-500,000 mPa·s at 25°C, or preferably about 50-10,000 or 5,000 mPa·s at 25°C. Oil with a viscosity, or glue with a molecular weight of approximately 1,000,000 mPa·s or higher at 25°C.

When they are cyclic organopolysiloxanes, they are formed from siloxane units "D" having the formulas Z ² ₂ SiO _2/2 and Z ³ HSiO _2/2 , which may be dialkylsilane Oxygen type or only unit Z ³ HSiO _2/2 . They then have a viscosity of approximately 1 to 5,000 mPa·s.

Examples of linear silicon-hydrogen bonded organopolysiloxane compounds B are: dimethylpolysiloxane with hydrogen dimethylsilyl end groups, dimethylhydrogen with trimethylsilyl end groups Methylpolysiloxane, dimethylhydromethylpolysiloxane with hydrogendimethylsilyl end groups, hydromethylpolysiloxane with trimethylsilyl endgroups, and cyclic Like hydrogen methyl polysiloxane.

Oligomers and polymers corresponding to the general formula (B.3) are particularly preferred as silicon hydrogen bond-containing organopolysiloxane compounds:

in:

·x and y are integers from 0 to 10,000,

·The symbols R ¹ may be the same or different and represent independently of each other:

o Linear or branched alkyl groups containing 1 to 8 carbon atoms, optionally substituted by at least one halogen, preferably fluorine, the alkyl groups are preferably methyl, ethyl, propyl, octyl and 3,3,3 -trifluoropropyl, or

oCycloalkyl groups containing 5-8 cyclic carbon atoms.

oAralkyl groups with an alkyl moiety containing 5 to 14 carbon atoms and an aryl moiety containing 6 to 12 carbon atoms.

The following compounds are particularly suitable for use in the present invention as silicon-hydrogen bonding organopolysiloxane compounds:

where a’, b’, c’, d’ and e’ are defined as follows:

·In the polymer of formula S1:

·0≤a’≤150, preferably 0≤a’≤100, and more particularly 0≤a’≤20, and

·1≤b’≤90, preferably 10≤b’≤80 and more particularly 30≤b’≤70,

·In the polymer of formula S2: 0≤c’≤15

· In the polymer of formula S3: 5≤d’≤200, preferably 20≤d’≤100, and

2≤e'≤90, preferably 10≤e'≤70.

As a further alternative, it is also possible to use at least one organopolysiloxane resin having at least two hydrogen atoms per molecule bonded to the same or different silicon atoms.

The organopolysiloxane resin contains:

a) At least two different siloxane units, which are selected from the siloxane unit M represented by the formula R ₃ SiO _1/2 , the formula R ₂ SiO _2/2 siloxane units D represented by the formula RSiO _3/2 , siloxane units T represented by the formula RSiO 3/2 and siloxane units Q represented by the formula SiO _4/2 , wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and

b) Provided that at least one of these siloxane units is a siloxane unit T or Q, and at least one of the siloxane units M, D and T contains a siloxane group.

Therefore, according to a preferred embodiment, the organopolysiloxane resin may be selected from the following group:

- Organopolysiloxane resin of formula M’Q, which basically consists of the following units:

(a) Monovalent siloxane units M' of the formula (R ₂ ) (H)SiO _1/2 , and

(b) is a tetravalent siloxane unit Q of the formula SiO _4/2 , and

- Organopolysiloxane resin of formula MD’Q, which basically consists of the following units:

(a) Divalent siloxane unit D' of formula (R)(H)SiO _2/2 ,

(b) monovalent siloxane units M of formula R ₃ SiO _1/2 , and

(c) Tetravalent siloxane unit Q of the formula SiO _4/2 ,

Wherein R represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably a monovalent aliphatic or aromatic hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms.

Furthermore, as yet another alternative, at least one linear organopolysiloxane having at least one hydrogen atom per molecule bonded to the same or different silicon atom and at least one linear organopolysiloxane having at least one hydrogen atom per molecule bonded to the same or different silicon atom may be used. A mixture of organopolysiloxane resins having hydrogen atoms on the same or different silicon atoms serves as component (B). In this case, linear organopolysiloxanes and polysiloxane resins can be mixed in any ratio within a wide range, which can be based on the desired product properties such as hardness and the silicon-hydrogen to alkene group ratio. Wait to adjust.

Although in practice it is common to use at least one organopolysiloxane containing at least two alkenyl groups per molecule bonded to silicon atoms, and at least one organopolysiloxane having at least two alkenyl groups per molecule bonded to the same or different silicon atoms, respectively, Organopolysiloxanes with hydrogen atoms on the atoms, as component (A) or (B) or the main component of both components, but theoretically it is not excluded that they can be used at the same time in the polysiloxane chain. Polymers with small amounts of alkenyl and silyl groups, in which case such polysiloxanes with small amounts of alkenyl and silyl groups are generally classified as component (B).

(C)Platinum catalyst

Catalysts consisting of at least one metal or compound from the platinum group are well known. The metals of the platinum group are those known by the name platinum group metals, a term that includes, in addition to platinum, ruthenium, rhodium, palladium, osmium and iridium. Preference is given to using platinum and rhodium compounds, complexes of platinum and organic products with 1,3-divinyltetramethyldisiloxane, containing the aforementioned Compounds of silicone resin powders of catalysts, rhodium compounds, such as those represented by the following formula: RhCl(Ph ₃ P) ₃ , RhCl ₃ [S(C ₄ H ₉ ) ₂ ] ₃ , etc.; tetrakis(triphenyl) Palladium, a mixture of palladium black and triphenylphosphine, etc.

The platinum catalyst should preferably be used in a catalytically sufficient amount to allow sufficiently rapid cross-linking at room temperature. Typically, 1 to 1,000 ppm by weight of catalyst is used, preferably 10 to 100 ppm by weight, more preferably 10 to 50 ppm by weight relative to the total silicone composition, based on the amount of Pt metal.

(D) Reinforcement filler

In order to obtain sufficiently high mechanical strength, it is advantageous to include silica fine particles, which are at least partially surface-treated, as reinforcing fillers in the addition-crosslinkable silicone composition. Precipitated and fumed silicas and mixtures thereof can be used. The specific surface area of these reactive reinforcing fillers should be at least 50 m ² /g, preferably 100 to 400 m ² /g, as determined by the BET method. This reactive reinforcing filler is a very well-known material in the field of silicone rubber. The silica filler may be hydrophilic or may be hydrophobized by known methods. Advantageously, the silica reinforcing filler is integrally surface treated. This means that at least 50%, more preferably at least 80% or at least 90% or especially preferably the entire surface of the silica reinforcing filler surface is preferably hydrophobically treated.

In a preferred embodiment, the silica reinforcing filler is fumed silica having a specific surface area of at least 50 m ² /g, and preferably from 100 to 400 m ² /g, as determined by the BET method. Fumed silica with a hydrophobic surface treatment can be used. In those cases, if fumed silica with a hydrophobic surface treatment is used, fumed silica with a preliminary hydrophobic surface treatment can be used, or in the process of mixing the fumed silica with the organopolysiloxane Surface treatment agents are added to allow for in-situ treatment of fumed silica.

The surface treatment agent may be selected from any conventionally used agent, such as alkylalkoxysilanes, alkyl chlorosilanes, alkyl silazanes, silane coupling agents, titanate-based treatments, and fatty acid esters, and may Use a single treatment or a combination of two or more treatments, either simultaneously or at different times.

The amount of silica reinforcing filler in the addition crosslinkable silicone composition is from 2 to 40 wt%, preferably from 5 to 35 wt%, and more preferably from 10 to 30 wt%, based on the weight of the total composition. If the blending amount is less than 2wt%, sufficient elastomer strength may not be obtained and collapse will not be significantly reduced; while if the blending amount exceeds 40wt%, the actual blending process may become difficult. More preferred amounts as described above will result in more significant improvements in collapse, deformation and workability.

(E) Cross-linking inhibitor

Cross-linking inhibitors are optional components. However, they are commonly used in addition-crosslinked silicone compositions to slow the cure of the composition at ambient temperatures. Inhibitors can be selected from the following compounds:

·Alkylenic alcohols, such as ethynylcyclohexanol,

·Tetramethylvinyltetrasiloxane, such as 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane

·Pyridine,

·Organophosphines and phosphites,

· Unsaturated amides, and

·Alkyl maleate.

Acetylenic alcohols (see FR1528464B and FR2372874A) are preferred thermal retardants for hydrosilylation reactions and have the following formula:

(R')(R")(OH)C-C≡CH

Where: R' is a linear or branched alkyl group, or phenyl; and R" is H or a linear or branched alkyl group, or phenyl; the groups R' and R" and the α position relative to the triple bond Carbon atoms can form rings. The total number of carbon atoms contained in R' and R" is at least 5 and preferably 9-20.

For the acetylenic alcohols, examples that may be mentioned include:

·1-ethynyl-1-cyclohexanol;

·3-Methyl-1-dodecyn-3-ol;

·3,7,11-trimethyl-1-dodecyn-3-ol;

·1,1-diphenyl-2-propyn-1-ol;

·3-ethyl-6-ethyl-1-nonyn-3-ol;

·2-Methyl-3-butyn-2-ol;

·3-Methyl-1-pentadecene-3-ol; and

· Diallyl maleate or diallyl maleate derivatives.

In a preferred embodiment, the inhibitor is 1-ethynyl-1-cyclohexanol.

To obtain a longer working time or "pot life," the amount of inhibitor is adjusted to achieve the desired "pot life." The concentration of catalyst inhibitor in the present silicone composition is sufficient to slow the curing of the composition at ambient temperatures. This concentration will vary widely depending on the specific inhibitor used, the nature and concentration of the hydrosilylation catalyst, and the nature of the silicon-hydrogen bonding polydimethylsiloxane. In some cases, inhibitor concentrations as low as 1 mole of inhibitor per mole of platinum group metal will produce satisfactory storage stability and cure rates. In other cases, each mole of platinum group metal may Inhibitor concentrations as high as 500 moles or more of inhibitor can be required. The optimal concentration of inhibitor in a given silicone composition can be readily determined by routine experimentation.

Advantageously, the amount of crosslinking inhibitor in the addition crosslinkable silicone composition is 0.01% to 2% by weight, preferably 0.03% to 1% by weight, relative to the total amount of the silicone composition. Weight scale.

The use of inhibitors effectively avoids premature solidification of the silicone composition on the nozzle tip and subsequent deformation of the printed layer.

(F)Thixotropic agent

The thixotropic agent of the present invention can be selected from phenyl-containing compounds, epoxy group-containing compounds, ester group-containing compounds, ether group-containing compounds, etc. These compounds can be connected to polysiloxane or to hydrocarbon groups, and can be small molecule compounds or polymers. Phenyl-containing compounds are preferred, and phenyl-containing polysiloxanes are more preferred.

Organopolysiloxanes E having aryl groups are organopolysiloxanes containing at least one siloxane unit with an aryl group directly connected to a Si atom.

In a preferred embodiment, the organopolysiloxane having aryl groups is an organopolysiloxane containing siloxanyl units of formula (F-1):

[R ⁵ _p R ⁶ _q SiO _(4-pq)/2 ] _n (F-1)

in:

R ⁵ and R ⁶ are independently selected from each other from hydrocarbon-based groups containing 1 to 30 carbon atoms and hydrogen;

in:

n is an integer greater than or equal to 1;

p and q are independently 0, 1, 2 or 3; and

p+q=1, 2 or 3;

The proviso is that the organopolysiloxane having aryl groups contains at least one aryl group directly connected to a Si atom.

In a preferred embodiment, the organopolysiloxane consists essentially of siloxane units of formula (F-1).

In a preferred embodiment, the hydrocarbon-based group contains from 1 to 24, preferably from 1 to 18, more preferably from 1 to 12, for example from 2 to 8 carbon atoms. The hydrocarbon-based groups may include linear, branched or cyclic alkyl or alkenyl groups, which are unsubstituted or substituted with one or more halogen and aryl groups, and aryl groups, which Is unsubstituted or substituted with one or more halogens and C ₁ -C ₆ alkyl and contains 6 to 12 carbon atoms.

The organopolysiloxane has a linear, branched or cyclic structure, and is preferably linear. Online linear or branched structures , the organopolysiloxane may be terminated by an -R or -SiR ₃ group, where R independently of one another has the meaning given for the R ⁵ and R ⁶ groups. Those skilled in the art will understand that aryl groups may be present laterally on the main chain of the organopolysiloxane or at the end of the chain as a capping group R or included in the capping group _-SiR3 .

In a preferred embodiment, the aryl group may be unsubstituted or substituted with one or more halogens and C ₁ -C ₆ alkyl and contain 6 to 12 carbon atoms. More preferably, they are selected from xylyl, tolyl and phenyl groups, most preferably phenyl.

In a preferred embodiment, in the above formula (F-1):

n is an integer greater than or equal to 2.

In a preferred embodiment, in the above formula (F-1):

p and q are 1 or 2 independently of each other.

In a preferred embodiment, in the above formula (F-1):

At least one of the groups R ⁵ and R ⁶ is an aryl group and the remainder is selected from an alkyl group containing 1 to 8 carbon atoms, preferably methyl or ethyl, and an alkenyl group containing 2 to 6 carbon atoms, preferably vinyl. .

In another preferred embodiment, the organopolysiloxanes having aryl groups, for example of the formula (F-1), contain at least one aryl group, preferably phenyl, and at least one alkenyl group, preferably ethylene. base.

In another preferred embodiment, organopolysiloxanes having aryl groups, for example of formula (F-1), contain at least one aryl group, preferably phenyl, and at least one SiH group.

In another preferred embodiment, the organopolysiloxanes having aryl groups, for example of the formula (F-1), contain at least one aryl group, preferably phenyl, and at least one alkenyl group, preferably vinyl. and at least one SiH group.

Taking into account the improvement of rheological properties and compatibility, especially in order to further avoid oil bleeding and improve transparency (which can be very important for silicone elastomer products), it is advantageous for organopolysiloxane E in addition to aromatic groups The group also contains at least one alkenyl group, preferably vinyl or SiH group. Alternatively, the organopolysiloxane additionally contains alkenyl groups and Si-H groups. Aryl and alkenyl groups and optionally hydrogen can be bonded directly to the same or different Si atoms, ie in the same or different siloxane units. Preferably, an alkenyl group, more preferably a vinyl group, is the end-capping group of the organopolysiloxane chain.

In an advantageous embodiment, the organopolysiloxanes having aryl groups contain or consist of organopolysiloxanes of the above formula (F-1) terminated by groups -R or -SiR ₃ Composed of siloxane units.

As useful examples of organopolysiloxanes E having aryl groups there may be mentioned compounds of the formula:

Methods for preparing organopolysiloxanes having aryl groups and preferably alkenyl groups are well known in the art and are known, for example, from CN105778102A, CN108329475A, CN106977723A, CN105778102A, CN101885845A, CN104403105A and CN103012797A.

In the present invention, the silicone composition contains 0.3-30 wt%, preferably 0.8-20 wt%, more preferably 1.0-10.0 wt% and most preferably 1.0-7.0 wt% of at least one organopolysiloxane having an aryl group. Alkane F, relative to the total weight of the silicone composition. In particular, if the content of organopolysiloxane F having aryl groups is below 7.0 wt% or even below 6.5 wt% or 6.0 wt%, the transparency of the composition can be further maintained at the desired level, which Might be especially useful in some applications.

Furthermore, advantageously the organopolysiloxanes having aryl groups have a viscosity of 3 to 10,000,000 mPa·s, preferably 10 to 200,000 mPa·s, for example 50 to 100,000 mPa·s and 100 to 10,000 mPa·s. Organopolysiloxanes having aryl groups have a refractive index greater than 1.405, preferably from 1.41 to 1.6, more preferably from 1.43 to 1.58.

The amount of aryl groups is therefore from 2 to 70% by weight, preferably from 5 to 62% by weight, and for example from 10 to 58% by weight, based on the total weight of the organopolysiloxane having aryl groups.

The individual components of the photocurable silicone composition are described in detail below.

(A’) Acrylate group-containing organopolysiloxane

The acrylate group-containing organopolysiloxane in the silicone composition of the present invention may have the following formula (A.3):

M*Dx M* (A.3)

in:

·M* is R ¹ (R) ₂ SiO _1/2 ;

·D is (R) ₂ SiO _2/2 ;

·x≥60, preferably 60≤x≤500, most preferably 90≤x≤400;

R is an alkyl group selected from methyl, ethyl, propyl, trifluoropropyl and phenyl, most preferably R is methyl;

R ¹ is a structural moiety having the general formula -C _n H _2n O-CH ₂ CHR ² (CH ₂ ) _m -OCOCH=CHR ³ , where n is 3 or 4, and m is 0 or 1, preferably m is 1 , R ² is H, OH or -C _z H _2z -CH ₂ OH, z is 0, 1, 2 or 3, and R ³ is H or -CH ₃ .

The organopolysiloxane in the silicone composition of the present invention may also have the following formula (A.4):

M D _v (D ^ACR ) _w M (A.4)

in:

·M is R ² (R) ₂ SiO _1/2 ; (R) ₃ SiO _1/2 or R ⁴ (R) ₂ SiO _1/2 ;

·D is (R) ₂ SiO _2/2 ;

·D ^ACR is (R ² )(R)SiO _2/2 ;

·y is 0-500, preferably 10-500, most preferably 50-400,

·w is 0-50, preferably 1-25, most preferably 3-20, when w=0, y is 1-500, and M represents R ² (R) ₂ SiO _1/2 or R ⁴ (R) ₂ SiO _1/2 ;

R is an alkyl group selected from methyl, ethyl, propyl, trifluoropropyl and phenyl, most preferably R is methyl;

· R ² is a structural part with the following general formula:

oC _n H _2n O-CH ₂ CHR ² (CH ₂ ) _m -OCOCH=Structural moiety of CHR ³ , where n is 3 or 4, and m is 0 or 1, and R ² is H, OH, or -C _z H _2z -CH ₂ OH, z is 0, 1, 2, or 3, and R ³ is H or -CH ₃ ; or

oC _n H _2n O-COCH=CHR ³ , where n is 3 or 4, and R ³ is H or -CH ³ ;

·R ⁴ is a structural part with formula (A.5):

The acrylate group-containing organopolysiloxane in the silicone composition of the present invention includes an organopolysiloxane with an acrylate group located on the side group and an organopolysiloxane with an acrylate group located in the middle, which contains at least two acrylic acids. Ester groups, preferably at least three acrylate groups.

(C’) Photoinitiator

Suitable examples of photoinitiators include acylphosphine oxides or acylphosphine oxides. Solvents can be used in combination with photoinitiators, such as isopropyl alcohol, to dissolve into the silicone composition.

A suitable photoinitiator in this invention is Norrish Type I, which cleaves to produce free radicals when irradiated with UV light. Preferred photoinitiators are derivatives of phosphine oxide, such as:

Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO)

Ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate (TPO-L)

Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO)

CPO-1 and CPO-2 can be prepared according to the protocol described in Molecules 2020,25(7),1671, New Phosphine Oxides as High Performance Near UV Type I Photoinitiators of Radical Polymerization.

Other suitable photoinitiators are liquid bisacyl aluminum oxides, such as described in US2016/0168177A1, or acylphosphines, such as those described in US2008/0004464.

The most preferred photoinitiator is ethyl phenyl(2,4,6-trimethylbenzoyl)phosphinate (TPO-L).

(D) Reinforcement filler

The reinforcing filler may be the same reinforcing filler used in the above addition type silicone composition.

(G)Other components

The silicone compositions according to the present invention may also contain other additives, such as standard semi-reinforced or filled fillers, other functional silicone resins such as silicone resins with vinyl groups, non-reactive methylpolysiloxanes, pigments or binders accelerator.

Non-siliceous minerals that may be included as semi-reinforcing or filling mineral fillers may be selected from: carbon black, titanium dioxide, alumina, hydrated alumina, calcium carbonate, ground quartz, diatomaceous earth, zinc oxide, mica, talc, Iron oxide, barium sulfate and hydrated lime.

Silicone sheets or silicone parts

The second aspect of the invention relates to 3D printed silicone sheets or composite sheets.

"Silicone sheet" refers to a cured product formed from silicone, with any size that can be formed by 3D printing, with regular or irregular shapes, which can have flat, curved, undulating surfaces, or hollows Structure.

"Composite" refers to an article that contains silicone parts and other materials, such as traditional wearable fabrics.

"Silicone part" refers to the cured part of the composite material formed from silicone, which part has any size that can be formed by 3D printing, has a regular or irregular shape, and can have a flat, curved, undulating surface, It can also have a hollow structure.

The thickness of the silicone part of the silicone sheet or composite sheet of the present invention is 0.1-15mm, preferably 0.2-10mm, more preferably 0.4-5mm, more preferably 0.4-2mm.

The silicone part of the silicone sheet or composite sheet of the present invention has the following properties:

Shore A hardness: 10-90, preferably 30-80, more preferably 40-70;

Tear strength: ≥3N/mm, preferably ≥10N/mm;

Tensile strength: ≥2Mpa, preferably ≥4Mpa;

Elongation at break: ≥50%, preferably ≥75%, more preferably ≥150%.

Each printed layer of the silicone part of the silicone sheet or composite sheet of the present invention can have the same or different patterns from each other, so as to have a more three-dimensional and aesthetic feeling. The same or different patterns come from the way each layer stacks up the same or differently from each other.

Due to the above properties, the silicone sheet or composite sheet of the present invention is suitable for use in manufacturing wearable consumer products.

3D printing methods

The printing method applicable to the present invention is not limited, and may be an extrusion method, a photocuring method (DLP, SLA, etc.), a jet method, etc. Thermal or light radiation can be applied during the printing process or after printing.

The process of extrusion printing, for example, includes adding the silicone composition of the present invention into a printing rubber cylinder, and different silicone sheets can be printed based on the designed patterns through, for example, an extrusion printer.

The process parameters of the extrusion 3D printing method include, for example: the diameter of the extrusion head is 0.25-0.4mm, the filling ratio is 100%, the printing speed is 15-25mm/s, and the layer thickness is 0.2-0.3mm. After the material is printed, it is cured at room temperature or heated according to the curing process requirements, or cured while printing.

The process of light-curing printing includes, for example, pouring the silicone material into the squeegee groove, adjusting the gap between the squeegee and the release film; importing the printing model, setting the slicing parameters, exporting the print file to the printer; and setting the exposure intensity and exposure time of each layer. , and then start printing layer by layer; perform secondary curing of the printed model.

Different 3D printing technologies have different design points. Design features include but are not limited to honeycomb structure, triangle, rectangle, star and other structural units, and each printing layer can have the same or different patterns according to personalized customization requirements, increasing the three-dimensional sense and beauty of the material. A single characteristic thickness is at least one layer thickness, preferably at least 3 layer thicknesses. Taking 3 layer thicknesses as an example, if one layer thickness is 0.1mm, the thickness of a single feature is at least 0.3mm). Moreover, the minimum line width of the structural design is 0.1-5mm, preferably 0.5-1.6mm, and the minimum island or island shape area is not less than 1mm ² , preferably not less than 6mm ² .

Select a silicone material with appropriate hardness for 3D printing. The printer has at least two nozzles that can print two-component liquid silicone and a support material. The support material can be water-soluble. Each nozzle has a cut-off system, and one of the nozzles has an up and down avoidance function, which can support and assist printing of complex feature structures, thus meeting the design requirements of wearable consumer products such as clothing.

Silicone fabric

A third aspect of the invention relates to silicone fabrics suitable for the manufacture of wearable consumer products.

"Silicone fabric" refers to materials made of silicone materials alone or in composite materials with other materials, and are suitable for manufacturing wearable consumer products such as clothing, shoes, hats, bags and accessories.

The silicone fabric is made by splicing two or more silicone sheets or composite sheets of the present invention with the same or different patterns. The splicing method includes sewing, knitting, weaving, bonding, and buttoning. It is equivalent to any conventional splicing method in the field of wearable consumer products.

Wearable consumer goods

A fourth aspect of the invention relates to silicone sheets or composite sheets by the method of the invention or utilizing the invention. Wearable consumer products made of materials, such as clothing, shoes, hats, bags and accessories.

Align the silicone sheets of the present invention in a specified manner, and select an appropriate method to splice them into a silicone fabric. It can then be bent or spliced together with traditional wearable fabrics to form the final customized wearable consumer product. The splicing methods include sewing, knitting, weaving, bonding, fastening and other conventional splicing methods in the field of wearable consumer products.

The composite sheet of the present invention can also be used to manufacture wearable consumer products, forming the entirety or part thereof.

Example

In order to illustrate the present invention more clearly, the following examples are enumerated, but they do not limit the present invention in any way.

The raw materials used in the examples are listed in Table 1 below.

Table 1 Raw material structure description

Example 1-3

The preparation process of Example 1 is as follows: all raw materials are mixed according to weight ratio, and 58.8 parts of vinyl-terminated polydimethylsiloxane A-1, 3.84 parts of A-2 and 7.5 parts of B-1 are mixed under stirring. Then 25.2 parts of D-1, 2 parts of E-1 and 0.15 parts of E-2 were added to the above mixture, followed by adding 2.5 parts of F-1 under stirring. Finally, 0.01 part of catalyst C-1 was added.

Embodiments 2 and 3 were also prepared according to the above process, and the raw material ratio is shown in Table 2.

Example 4-5

The preparation process of Example 4 is as follows: all raw materials are mixed in a weight ratio of 48.46 parts of acrylate-terminated polydimethyl Silicone A'-1 was mixed with 3.07 parts of acrylate-grafted polydimethylsiloxane A'-2. 23.09 parts of G-1 were added and stirred, followed by 24.61 parts of silica D-2. Finally, 0.77 parts of C'-1 was added to the mixture in portions.

Embodiment 5 was also prepared according to the above process, and the raw material ratio is shown in Table 2.

3D printing process

The silicone compositions of Examples 1-3 were 3D printed based on the ink direct writing 3D printing process using a Sandraw S300 extrusion 3D printer and following the following procedures:

1. Load the printing materials shown in Table 2 into the extruder;

2. Adjust the printing platform horizontally and set the following printing parameters:

Extruder head diameter: 0.4mm

Fill rate: 95%

Extrusion rate: 85%

Printing speed: 20mm/s

3. Extrude the printing material and deposit it layer by layer for printing.

The 3D printing process of the silicone composition of Example 4-5 based on photopolymerization is as follows:

1. First, completely remove the bubbles from the freshly prepared single silicone composition material in the example;

2. The forming table and the ink cartridge are installed firmly, and make sure that the release film on the ink cartridge and the bottom transparent glass are clean and free of foreign matter;

3. Check and install the scraper;

4. Pour the silicone material into the scraper groove, and adjust the gap between the scraper and the release film to be within the range of about 0.2-0.3mm;

5. Import the printing model, set the slicing parameters, and export the printing file to the printer;

6. Set the exposure intensity and exposure time of each layer according to the optimized single-layer exposure parameters, and then start printing layer by layer;

7. After printing is completed, take out the printed model;

8. Place the printed model into an oven at 80°C to 150°C for secondary curing until the surface is completely solidified and the color remains unchanged.

Performance evaluation

The results of the sample evaluation based on the curing method according to the present invention are listed in Table 2.

Hardness: The hardness of cured samples based on the curable silicone composition was measured in accordance with ASTM D2240 at 25°C. Details of the measurement conditions are listed in Table 2. Cured samples based on the photocurable silicone composition were obtained under a DLP printing process at 25°C and UV irradiation at 405 nm. Then post-cure under heating conditions at 150°C for 1 hour.

Tensile Strength and Elongation at Break: The tensile strength and elongation at break of cured samples based on the curable silicone composition were measured at 25°C in accordance with ASTM D412. Details of the measurement conditions are listed in Table 2. Details of the measurement conditions are listed in Table 2. Cured samples based on the photocurable silicone composition were obtained under a DLP printing process at 25°C and UV irradiation at 405 nm. Then post-cure under heating conditions at 150°C for 1 hour.

Tear Strength: The tear strength of cured samples based on the curable silicone composition was measured in accordance with ASTM D642 at 25°C. Details of the measurement conditions are listed in Table 2. Cured samples based on the photocurable silicone composition were obtained under a DLP printing process at 25°C and UV irradiation at 405 nm. Then post-cure under heating conditions at 150°C for 1 hour.

Table 2 Silicone composition formula and test results

Example 6

First, design a lightweight 3D model containing different filling unit structures or texture features. Referring to the design principles, the design thickness of this embodiment is 1.2mm, and the design width of a single line or area is ≥ 1.6mm. At the same time, considering the limited printing size, post-processing is added during the design. Glue the alignment allowance and then export the data in STL format.

After inspecting and repairing the STL model, select a 0.4mm extrusion nozzle and appropriate process parameters for parametric slicing. Key process parameters such as scanning speed of 18mm/s, layer thickness of 0.2mm, filling rate of 100%, and material supply rate is 80%.

Import the slice data to a printer. The printer is an extrusion printer with two nozzles. It can print the main body and the auxiliary support material. The main body material is the silicone composition from Example 2. The support material is soluble in water. One of the extrusion nozzles of the printer has a Z-axis avoidance function. Wait for the device to level automatically and then start printing until it ends.

Place the printed silicone sample in an 80°C oven, heat and cure for 30-60 minutes, then raise the temperature to 120°C and heat and cure for 15 minutes to complete the curing and molding of the sample.

Fix the cured 3D printed silicone samples on the fluorine film in sequence, then use Elkem's SILBIONE MED ADH 4213 two-component adhesive to align the printed silicone samples and apply them evenly, and use the fluorine film on the upper layer Isolate, protect and compact, and finally place it in an oven at 120°C for heating and curing for 15-30 minutes and take it out.

Take XG-039G:D70A=1:5. During the dispersion process, add 3% platinum curing agent PEM001 based on the input amount of XG-039G. After evenly dispersed, it can be sprayed on the 3D printed silicone sheet at 180°C Bake for 10 minutes to obtain the post-processed silicone sheet. (Note: XG-039G, D70A and platinum curing agent PEM001 are all from Elkem Silicones (Guangdong) Co., Ltd.)

Post-processed silicone sheets have a smooth feel. The post-processed silicone sheets are then made into garments along with textiles.

Example 7

First, design a lightweight 3D model containing different filling unit structures or texture features. Referring to the design principles, the design thickness of this embodiment is 0.6mm, and the design width of a single line or area is ≥ 0.5mm. At the same time, considering the limited printing size, post-processing is added during the design. Glue the alignment allowance and then export the data in STL format.

After inspecting and repairing the STL model, select appropriate process parameters for parametric slicing. Key process parameters include exposure intensity of 50mw/mm ² , exposure time of 5s, and layer thickness of 0.1mm.

Import the slice data to the printer and start printing until the end. The printer is an inverted DLP light-curing printing Machine, surface exposure can greatly increase the printing speed, the host material is the silicone composition from Example 4, and the printer can add resin materials as needed.

Post-processing of the printed silicone sample can first use organic solvents such as ethanol for ultrasonic cleaning to remove residual resin on the surface, and then use UV for secondary curing for 15-30 minutes or place it in a 100-120°C oven for heating and curing for 30 minutes until it is completely formed.

Fix the cured 3D printed silicone samples on the fluorine film in sequence, then use Elkem's SILBIONE MED ADH 4213 two-component adhesive to align the printed silicone samples and apply them evenly, and use the fluorine film on the upper layer Isolate, protect and compact, and finally place it in an oven at 120°C for heating and curing for 15-30 minutes and take it out.

Silicone samples are post-processed and then combined with synthetic materials into packages.

Claims (27)

A method for additive manufacturing of wearable consumer products, the method comprising the following steps: 1) 3D print the silicone composition into silicone sheets; 2) Use the silicone sheet to manufacture wearable consumer products. The method of claim 1, wherein each printed silicone layer of the silicone sheet has the same or different patterns from each other. The method according to claim 1 or 2, wherein using the silicone sheet in step 2) to manufacture wearable consumer products includes making the silicone sheet into a wearable consumer product alone or together with a wearable fabric. Made into wearable consumer products. The method according to any one of claims 1 to 3, wherein using the silicone sheet in step 2) to manufacture wearable consumer products includes combining two or more of the silicone sheets with the same or different patterns from each other. The above-mentioned silicone sheets are spliced and then used to manufacture wearable consumer products. A method for additive manufacturing of wearable consumer products, the method comprising the following steps: 1) 3D print the silicone composition into a composite sheet on the wearable fabric substrate; 2) Use the composite sheet to manufacture wearable consumer products. The method according to claim 5, wherein using the composite sheet in step 2) to manufacture wearable consumer products includes manufacturing the composite sheet into a wearable consumer product alone or together with a wearable fabric to make a wearable consumer product. consumer goods. The method of claim 5 or 6, wherein each printed silicone layer of the composite sheet has the same or different patterns from each other. The method according to any one of claims 5-7, wherein in step 2), the composite sheet is used for Manufacturing wearable consumer products includes splicing two or more composite sheets with the same or different patterns to each other, and then using them to manufacture wearable consumer products. The method according to any one of claims 1 to 8, wherein the 3D printing is performed using a 3D printer with at least two nozzles, one of which prints the support material, and the other nozzles print the silicone composition, and the step 1) also includes removing the support material. The method according to any one of claims 1-9, wherein the 3D printing is extrusion 3D printing, and the silicone composition is an addition-type silicone composition comprising the following components in a weight ratio:
The method according to any one of claims 1 to 9, wherein the 3D printing is light-curing 3D printing, and the silicone composition is a light-curing silicone composition comprising the following components in a weight ratio:
The method according to any one of claims 1 to 11, wherein the silicone sheet or the silicone portion of the composite sheet is post-treated to improve surface quality, wherein the post-treatment includes heating, radiation Illuminating, sanding, lasering, spraying or applying a thermal or UV curable silicone composition, or any combination of the foregoing. The method of any one of claims 1-12, wherein the wearable consumer products include clothing, shoes, hats, bags and accessories. The silicone sheet made in step 1) of the method of claim 1, wherein each printed silicone layer of the silicone sheet has the same or different patterns from each other. The silicone sheet according to claim 14, wherein the thickness of the silicone sheet is 0.1-15mm, preferably 0.2-10mm, more preferably 0.4-5mm, more preferably 0.4-2mm. The silicone sheet according to claim 14 or 15, wherein the Shore A hardness of the silicone sheet is 10-90, preferably 30-80, more preferably 40-70. The silicone sheet according to any one of claims 14 to 16, wherein the tear strength of the silicone sheet is ≥3 N/mm, preferably ≥10 N/mm. The silicone sheet according to any one of claims 14 to 17, wherein the tensile strength of the silicone sheet is ≥2Mpa, preferably ≥4Mpa. The silicone sheet according to any one of claims 14 to 18, wherein the silicone sheet has an elongation at break of ≥50%, preferably ≥75%, and more preferably ≥150%. The composite sheet made in step 1) of the method of claim 5, wherein each printed silicone layer of the composite sheet has the same or different patterns from each other. The composite sheet according to claim 20, wherein the silicone portion of the composite sheet has a Shore A hardness of 10-90, preferably 30-80, more preferably 40-70. The composite sheet of claim 21, wherein the silicone portion has a thickness of 0.1-15 mm, preferably 0.2-10 mm, more preferably 0.4-5 mm, more preferably 0.4-2 mm. The composite sheet according to claim 21 or 22, wherein the tear strength of the silicone part is ≥3 N/mm, preferably ≥10N/mm. The composite sheet according to any one of claims 22-23, wherein the tensile strength of the silicone part is ≥2Mpa, preferably ≥4Mpa. The composite sheet according to any one of claims 22 to 24, wherein the silicone portion has an elongation at break of ≥50%, preferably ≥75%, more preferably ≥150%. A silicone fabric suitable for manufacturing wearable consumer products, wherein the silicone fabric is formed by combining two or more silicone sheets according to any one of claims 14-19 with mutually identical or different patterns, or The composite sheets according to claims 20-25 are spliced together. Wearable consumer products containing silicone, the wearable consumer products preferably include clothing, shoes, hats, bags and accessories, wherein the wearable consumer products are made as follows: By a method according to any one of claims 1-7, or Utilize the silicone sheet according to any one of claims 8-12, or the composite sheet according to any one of claims 13-17, or the silicone fabric according to claim 26.